CN113171800B - 改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用 - Google Patents
改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用 Download PDFInfo
- Publication number
- CN113171800B CN113171800B CN202110443629.3A CN202110443629A CN113171800B CN 113171800 B CN113171800 B CN 113171800B CN 202110443629 A CN202110443629 A CN 202110443629A CN 113171800 B CN113171800 B CN 113171800B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- flexible ceramic
- ceramic nanofiber
- composite flexible
- nanofiber material
- 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.)
- Active
Links
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 245
- 239000002121 nanofiber Substances 0.000 title claims abstract description 174
- 239000000919 ceramic Substances 0.000 title claims abstract description 124
- 239000000463 material Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 168
- 239000012528 membrane Substances 0.000 claims abstract description 82
- 238000001354 calcination Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000005507 spraying Methods 0.000 claims abstract description 39
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 11
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000012266 salt solution Substances 0.000 claims description 36
- 239000000835 fiber Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- 230000003197 catalytic effect Effects 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 230000015556 catabolic process Effects 0.000 claims description 25
- 238000006731 degradation reaction Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 230000010412 perfusion Effects 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical group 0.000 claims description 5
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims 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 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 5
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 9
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 9
- 239000004299 sodium benzoate Substances 0.000 description 9
- 235000010234 sodium benzoate Nutrition 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 8
- 239000012429 reaction media Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical group [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000007590 electrostatic spraying Methods 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 238000009826 distribution Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000034655 secondary growth Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/143—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/62236—Fibres based on aluminium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
- C04B35/6224—Fibres based on silica
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
- D06M11/485—Oxides or hydroxides of manganese; Manganates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/49—Oxides or hydroxides of elements of Groups 8, 9,10 or 18 of the Periodic Table; Ferrates; Cobaltates; Nickelates; Ruthenates; Osmates; Rhodates; Iridates; Palladates; Platinates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/95—Products characterised by their size, e.g. microceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/963—Surface properties, e.g. surface roughness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Textile Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用,该方法是在同一接收基材上先后交替进行杂化纳米纤维膜的沉积和分子筛分散液的喷涂,并控制沉积次数比喷涂次数多一次后,进行煅烧处理制得复合柔性陶瓷纳米纤维材料;其中,杂化纳米纤维膜由包含陶瓷前驱体、高分子聚合物和溶剂的前驱体溶液经静电纺丝制得;制得的复合柔性陶瓷纳米纤维材料包含两层以上柔性陶瓷纳米纤维膜以及封装于相邻两层柔性陶瓷纳米纤维膜之间的分子筛。该材料可以用于氮氧分离;当分子筛上负载有活性组分时,该材料用于催化氧化降解工业废水。本发明的复合柔性陶瓷纳米纤维材料化学稳定性优异、比表面积大且制备简单,易于在工业中应用。
Description
技术领域
本发明属于工业催化用材料技术领域,具体涉及一种改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用。
背景技术
多相固体催化剂是目前工业中使用比例最高的催化剂,主要包括活性组分及载体两大部分,活性组分负载于载体之上,其中,载体材料应具有较高的比表面积和优良的物理化学稳定性。
近年来,分子筛因其比表面积大、内部孔道密集、稳定性好,在催化剂载体领域受到了广泛关注。然而,粉末或颗粒状分子筛间缺乏牢固的相互作用力,导致其在液相介质中使用时极易分散成悬浮液,使其面临与反应介质的分离成本高,操作复杂且易造成二次污染的问题,同时,其在空气介质中使用时存在易脱落、脆性大、不耐振动等问题。专利CN104874418B和CN103316708B经挤压成型后得到整体式分子筛催化剂,方便于反应介质分离,但其制备过程需要加入粘结剂,粘结剂会堵塞部分分子筛孔道使其无法被充分利用,催化活性降低;专利CN111841625A制备了一种不锈钢纤维复合分子筛膜处理VOCs催化剂,活性组分均匀分散在催化剂中,但其以不锈钢纤维为载体,采用水热二次生长法制备该材料,材料尺寸受反应釜内径限制,难以大规模、连续化生产;CN105603579B制备了一种高长径比中空分子筛纤维,但其将静电纺丝制备的纤维浸渍于分子筛晶种液中而后经水热合成制备了该材料,高温高压环境对纤维有很大损害,使其变脆变硬,且反应釜内径有限,限制了其规模化、连续化生产;美国专利US7390452B2公开了一种静电纺丝的介孔分子筛/纤维复合材料,聚醚酰亚胺(PEI)甲醇溶液和介孔分子筛溶液共混静电纺丝形成复合物,从扫描电子显微镜在纤维表面没有明显观察到分子筛,即分子筛大部分存在纤维中,内部的分子筛无法发挥其性能。
因此,研究一种可充分利用单分子筛的性能、催化性能优异、具备一定柔性、化学稳定性优异、比表面积大且制备简单、易于与反应介质相分离、易于在工业中实际应用的催化材料具有十分重要的意义。
发明内容
本发明的目的在于克服现有材料的不足之处,提供一种改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用。
为达到上述目的,本发明采用的技术方案如下:
一种改性分子筛复合柔性陶瓷纳米纤维材料,包含两层以上柔性陶瓷纳米纤维膜以及封装于相邻两层柔性陶瓷纳米纤维膜之间的分子筛。
作为优选的技术方案:
如上所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,柔性陶瓷纳米纤维膜的比表面积为40~200m2/g,厚度为10~100μm,纤维直径为100~600nm;改性分子筛复合柔性陶瓷纳米纤维材料中分子筛的含量为20~90wt%。
如上所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,柔性陶瓷纳米纤维膜为柔性二氧化硅纳米纤维膜或柔性二氧化钛纳米纤维膜;优选的二氧化硅和二氧化钛陶瓷纳米纤维膜均具有优异的亲水性,可与液相中有机污染物充分接触反应,且该材料耐腐蚀,化学稳定性好,可在复杂条件废水中长期使用而保持结构稳定。
如上所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,分子筛上还负载有活性组分;活性组分在分子筛上的负载量为3~65wt%。
如上所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,活性组分为金属氧化物;负载有活性组分的分子筛是通过将分子筛浸渍于金属盐溶液中后进行干燥和焙烧获得的;金属盐溶液中金属元素的含量为分子筛重量的5~80wt%;分子筛与金属盐溶液的质量比为1:10~100;浸渍时间为10~360min,温度为20~80℃;优选参数范围内,金属盐可充分溶解于溶剂中,而后通过浸渍、干燥并焙烧稳定负载于分子筛上,金属氧化物在分子筛上的负载量直接影响最终制备的负载催化剂的活性,该范围内制得的产品可保证其优异的催化活性。
如上所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,金属盐为硝酸铁、硫酸亚铁、硝酸锰、氯化锰、硝酸铜和硝酸钴中的一种以上;金属盐溶液中的溶剂为水和/或乙醇;
以上金属盐均具备水溶性或者醇溶性优良的特点,且原料易得,成本低廉,选择不同的金属盐直接影响最终制备的负载催化剂的活性,优选金属盐制得的产品可保证其优异的催化活性。
制备如上所述的一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,在同一接收基材上先后交替进行杂化纳米纤维膜的沉积和分子筛分散液的喷涂,并控制沉积次数比喷涂次数多一次后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
杂化纳米纤维膜由前驱体溶液经静电纺丝制得,前驱体溶液包含陶瓷前驱体、高分子聚合物和溶剂。
作为优选的技术方案:
如上所述的方法,陶瓷前驱体为正硅酸乙酯、硅酸钠、六甲基二氧硅烷、钛酸四丁酯、钛酸异丙酯和钛酸四乙酯中的一种以上;所选用的硅源和钛源在不同溶剂中,水解形成溶胶的过程有显著区别,直接影响纺丝成纤过程;
高分子聚合物为聚已烯醇、聚乙烯吡咯烷酮、聚氧化乙烯和聚乙烯醇缩丁醛中的一种以上;以上选择的聚合物均为水溶性和醇溶性较优异的聚合物,且原料易得,成本低廉,不同的聚合物会使最后成型陶瓷纤维具有多种独特的表面结构,得到不同形貌和比表面积的陶瓷纳米纤维;
前驱体溶液中的溶剂为水、冰乙酸、甲醇、乙醇、正丙醇、正丁醇、乙二醇、丙二醇、仲丁醇和N,N-二甲基甲酰胺中的一种以上;
前驱体溶液中,陶瓷前驱体的含量为10~50wt%,高分子聚合物的含量为1~10wt%;陶瓷前驱体含量以及高分子聚合物的浓度设定可以确保通过静电纺丝得到粗细均匀的纤维,同时,缓解煅烧过程中由于聚合物模板的去除,纤维膜的体积收缩对生产效率的影响;
静电纺丝的参数为:相对湿度25~55%,温度18~35℃,电压5~30kV,灌注速度0.1~10mL/h,纺丝距离10~40cm,滚筒速度5~100r/min,滑台运行速度5~100cm/min;
分子筛分散液中的溶剂为水、冰乙酸、乙醇和N,N-二甲基甲酰胺中的一种以上;负载有活性组分的分子筛分散液的浓度为10~50wt%;在该参数范围内,可制备静电喷涂所需的分子筛分散液,使负载有活性组分的分子筛喷涂于基材上,而后被稳定封装于相邻的纤维膜中,最终得到具有催化活性的且方便于反应介质相分离的固体催化材料;
喷涂采用静电纺丝装置;喷涂的参数为:相对湿度25~55%,温度18~35℃,电压10~30kV,灌注速度0.1~10mL/h,喷涂距离10~40cm,滚筒速度5~80r/min,滑台运行速度5~100cm/min;
煅烧的参数为:煅烧温度400~1000℃,升温速率2~10℃/min,保温时间0~6h;煅烧温度在400℃至1000℃之间且保温时间设置在0~6小时内可以确保金属盐完全分解,并且形成的金属氧化物结构较为完善;将升温速率控制在2~10℃/min内,金属氧化物颗粒生长较均匀,有效抑制升温速率不当引起的颗粒团聚,分布不均匀等情况。
本发明还提供如上所述的改性分子筛复合柔性陶瓷纳米纤维材料的应用,改性分子筛复合柔性陶瓷纳米纤维材料用于氮氧分离。
本发明还提供如上所述的改性分子筛复合柔性陶瓷纳米纤维材料的应用,改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水。
本发明的原理是:
在高压静电场作用下,陶瓷前驱体溶胶/聚合物液滴带电并且产生形变,在喷头末端处形成锥状液滴,当液滴表面静电斥力大于表面张力时,会使液滴表面喷射出溶液射流,在其飞行过程中经过溶液挥发、固化等过程最终形成杂化纳米纤维沉积在接收装置上;通过调控分子筛溶液体系,使其均匀分散,在高压作用下,以静电喷雾的形式将分子筛颗粒均匀负载到纤维表面,随后可以根据需求,将纤维和分子筛多次沉积,得到厚度可调的纤维-分子筛-纤维的三明治夹芯结构,最后通过高温煅烧得到复合材料。
本发明产品成型过程中仅使用静电纺丝设备(不需要静电雾化装置),仅使用柔性陶瓷纳米纤维膜作为外层基材使本发明制得的产品便于与反应介质相分离,负载有活性组分的分子筛通过静电喷涂的方式被纳米纤维膜封装于纤维层间而非纤维中,且外层材料为纳米纤维材料,孔隙率高且具备亲水性能,可与液相反应介质充分接触,液相反应介质可透过纤维膜间的孔隙与封装与其中的单分子筛充分接触、反应,可充分利用单分子筛的催化性能,有效比表面积大,催化活性位点多,催化效率高;因此,使得将本发明中的改性分子筛复合柔性陶瓷纳米纤维材料在应用至氮氧分离和催化氧化降解工业废水中时,取得了优异的效果。
有益效果
(1)本发明的一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,在材料成型过程中仅需要使用静电纺丝设备,无需额外静电喷涂设备,节约成本,减少设备占地面积;
(2)本发明一种改性分子筛复合柔性陶瓷纳米纤维材料的方法制备的材料结构为柔性陶瓷纳米纤维膜-分子筛-柔性陶瓷纳米纤维膜的类三明治结构,无需粘结剂即可将负载有活性组分的分子筛稳定封装于两层纳米纤维膜之中,不易脱落且不会对分子筛孔道结构产生破坏;
(3)本发明一种改性分子筛复合柔性陶瓷纳米纤维材料的方法制备的材料金属改性分子筛存在于纤维层间而非纤维中,且外层材料为纳米纤维材料,孔隙率高且具备亲水性能,可充分利用单分子筛的催化性能,有效比表面积大,催化活性位点多,催化效率高;
(4)本发明一种改性分子筛复合柔性陶瓷纳米纤维材料的方法制备的材料为整体式柔性催化材料,应用方便,便于与反应介质分离,无需进行二次处理。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明做各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(MCM41分子筛)浸渍于温度为20℃的金属盐溶液中360min后,进行干燥(干燥时间3h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为硝酸铁,溶剂为水;金属盐溶液中铁的含量为分子筛重量的10wt%;分子筛与金属盐溶液的质量比为1:10;
制得的负载有活性组分的分子筛中的活性组分为氧化铁;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为25wt%的正硅酸乙酯、含量为5wt%的聚已烯醇和水组成;
静电纺丝的参数为:相对湿度40%,温度20℃,电压18kV,灌注速度1mL/h,纺丝距离20cm,滚筒速度50r/min,滑台运行速度50cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在水中,制得浓度为30wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度40%,温度20℃,电压20kV,灌注速度1.5mL/h,喷涂距离20cm,滚筒速度40r/min,滑台运行速度50cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度800℃,升温速率5℃/min,保温时间0h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化硅纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为167m2/g,厚度为60μm,纤维直径为200~300nm;活性组分在分子筛上的负载量为9wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为50wt%。
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到90%,通过过硫酸盐氧化法1h内对苯酚的降解率达到89%。
测试方法如下:
臭氧催化氧化法降解苯甲酸钠:将50毫克的改性分子筛复合柔性陶瓷纳米纤维材料置于250mL圆底烧瓶中,向圆底烧瓶中加入100mL的100mg/L的苯甲酸钠模拟废水溶液,使用曝气头从圆底烧瓶底部曝气,将臭氧的进气流量控制在0.4L/min,进气浓度为4mg/L。连续曝气1小时后,取样,测定COD值,计算去除效果。
过硫酸盐氧化法:以50mg/L的苯酚溶液作为模拟废水,在100mL的苯酚模拟废水中加入20mM的过硫酸钾,取50mg的改性分子筛复合柔性陶瓷纳米纤维材料加至上述溶液中进行降解测试,以改性分子筛复合柔性陶瓷纳米纤维材料加入时作为计时零点,分别在60min取样,通过4-氨基安替比林法测试苯酚浓度,计算苯酚去除效果。
实施例2
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(钛硅分子筛TS-1)浸渍于温度为30℃的金属盐溶液中300min后,进行干燥(干燥时间3h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为硫酸亚铁,溶剂为水;金属盐溶液中铁的含量为分子筛重量的10wt%;分子筛与金属盐溶液的质量比为1:10;
制得的负载有活性组分的分子筛中的活性组分为氧化铁;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为20wt%的钛酸四丁酯、含量为2wt%的聚乙烯吡咯烷酮和质量比为7:5的乙醇与冰乙酸的混合物组成;
静电纺丝的参数为:相对湿度40%,温度30℃,电压15kV,灌注速度1.5mL/h,纺丝距离15cm,滚筒速度50r/min,滑台运行速度50cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在乙醇中,制得浓度为30wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度40%,温度30℃,电压25kV,灌注速度1.8mL/h,喷涂距离18cm,滚筒速度30r/min,滑台运行速度100cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度600℃,升温速率5℃/min,保温时间2h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化钛纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为156m2/g,厚度为30μm,纤维直径为200nm~300nm;活性组分在分子筛上的负载量为9.3wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为50wt%。
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到87%,通过过硫酸盐氧化法1h内对苯酚的降解率达到86%;测试方法如实施例1。
实施例3
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(13x分子筛)浸渍于温度为40℃的金属盐溶液中240min后,进行干燥(干燥时间3h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为硝酸铜,溶剂为水;金属盐溶液中铜的含量为分子筛重量的5wt%;分子筛与金属盐溶液的质量比为1:10;
制得的负载有活性组分的分子筛中的活性组分为氧化铜;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为20wt%的六甲基二氧硅烷、含量为1wt%的聚乙烯吡咯烷酮和甲醇组成;
静电纺丝的参数为:相对湿度55%,温度18℃,电压5kV,灌注速度0.1mL/h,纺丝距离10cm,滚筒速度5r/min,滑台运行速度5cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在冰乙酸中,制得浓度为10wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度55%,温度18℃,电压10kV,灌注速度0.1mL/h,喷涂距离10cm,滚筒速度5r/min,滑台运行速度5cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度400℃,升温速率2℃/min,保温时间2h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化硅纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为40m2/g,厚度为10μm,纤维直径为500~600nm;活性组分在分子筛上的负载量为3wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为20wt%。
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到85%,通过过硫酸盐氧化法1h内对苯酚的降解率达到85%;测试方法如实施例1。
实施例4
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(SAPO-34分子筛)浸渍于温度为50℃的金属盐溶液中180min后,进行干燥(干燥时间6h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为硝酸锰,溶剂为水;金属盐溶液中锰的含量为分子筛重量的20wt%;分子筛与金属盐溶液的质量比为1:40;
制得的负载有活性组分的分子筛中的活性组分为氧化锰;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为10wt%的硅酸钠、含量为5wt%的质量比为1:1的聚氧化乙烯与聚乙烯醇缩丁醛的混合物和N,N-二甲基甲酰胺组成;
静电纺丝的参数为:相对湿度40%,温度25℃,电压20kV,灌注速度10mL/h,纺丝距离40cm,滚筒速度100r/min,滑台运行速度100cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在水中,制得浓度为26wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度40%,温度25℃,电压30kV,灌注速度10mL/h,喷涂距离40cm,滚筒速度80r/min,滑台运行速度100cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度1000℃,升温速率3℃/min,保温时间2h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化硅纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为169m2/g,厚度为40μm,纤维直径为200nm~300nm;活性组分在分子筛上的负载量为18wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为48wt%。
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到92%,通过过硫酸盐氧化法1h内对苯酚的降解率达到93%;测试方法如实施例1。
实施例5
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(ZSM-5分子筛)浸渍于温度为60℃的金属盐溶液中120min后,进行干燥(干燥时间6h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为氯化锰,溶剂为乙醇;金属盐溶液中锰的含量为分子筛重量的80wt%;分子筛与金属盐溶液的质量比为1:60;
制得的负载有活性组分的分子筛中的活性组分为氧化锰;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为30wt%的质量比为1:1的正硅酸乙酯和硅酸钠的混合物、含量为10wt%的聚氧化乙烯和质量比为1:1的丙二醇和仲丁醇混合物组成;
静电纺丝的参数为:相对湿度35%,温度26℃,电压25kV,灌注速度1mL/h,纺丝距离16cm,滚筒速度20r/min,滑台运行速度30cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在N,N-二甲基甲酰胺中,制得浓度为32wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度35%,温度26℃,电压20kV,灌注速度5mL/h,喷涂距离16cm,滚筒速度20r/min,滑台运行速度20cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度700℃,升温速率6℃/min,保温时间3h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化硅纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为183m2/g,厚度为35μm,纤维直径为100~200nm;活性组分在分子筛上的负载量为62wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为57wt%。
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到99%,通过过硫酸盐氧化法1h内对苯酚的降解率达到98%;测试方法如实施例1。
实施例6
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(钛硅分子筛TS-1)浸渍于温度为80℃的金属盐溶液中10min后,进行干燥(干燥时间6h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为硝酸钴,溶剂为乙醇;金属盐溶液中钴的含量为分子筛重量的60wt%;分子筛与金属盐溶液的质量比为1:80;
制得的负载有活性组分的分子筛中的活性组分为氧化钴;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为50wt%的钛酸异丙酯、含量为7wt%的聚乙烯醇缩丁醛和正丙醇组成;
静电纺丝的参数为:相对湿度35%,温度35℃,电压30kV,灌注速度6mL/h,纺丝距离26cm,滚筒速度60r/min,滑台运行速度50cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在水中,制得浓度为38wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度35%,温度35℃,电压22kV,灌注速度7mL/h,喷涂距离26cm,滚筒速度55r/min,滑台运行速度40cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度800℃,升温速率7℃/min,保温时间4h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化钛纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为176m2/g,厚度为80μm,纤维直径为400~500nm;活性组分在分子筛上的负载量为37wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为65wt%。
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到96%,通过过硫酸盐氧化法1h内对苯酚的降解率达到95%;测试方法如实施例1。
实施例7
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)负载有活性组分的分子筛的制备;
通过将分子筛(ZSM-5分子筛)浸渍于温度为70℃的金属盐溶液中200min后,进行干燥(干燥时间36h,干燥温度110℃)和焙烧(焙烧温度550℃,焙烧时间2h)获得负载有活性组分的分子筛;金属盐溶液中,金属盐为质量比为1:1硝酸铁和硝酸锰的混合物,溶剂为质量比1:1的水和乙醇的混合物;金属盐溶液中铁和锰的含量为分子筛重量的40wt%;分子筛与金属盐溶液的质量比为1:100;
制得的负载有活性组分的分子筛中的活性组分为氧化铁和氧化锰;
(2)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为25wt%的钛酸四乙酯、含量为3wt%的聚已烯醇和正丁醇组成;
静电纺丝的参数为:相对湿度30%,温度20℃,电压10V,灌注速度2mL/h,纺丝距离14cm,滚筒速度10r/min,滑台运行速度10cm/min;
(3)将步骤(1)制得的负载有活性组分的分子筛分散在质量比为1:1的水和冰乙酸的混合溶液中,制得浓度为50wt%的负载有活性组分的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(2)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度30%,温度20℃,电压15kV,灌注速度3mL/h,喷涂距离13cm,滚筒速度10r/min,滑台运行速度10cm/min;
(4)在步骤(3)所得材料上,在喷涂分子筛分散液的那一面,依次重复步骤(2)、步骤(3)、步骤(2)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度500℃,升温速率10℃/min,保温时间6h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含3层柔性二氧化钛纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的负载有活性组分的分子筛;柔性陶瓷纳米纤维膜的比表面积为200m2/g,厚度为100μm,纤维直径为300nm~400nm;活性组分在分子筛上的负载量为65wt%;改性分子筛复合柔性陶瓷纳米纤维材料中负载有活性组分的分子筛的含量为90wt%;
应用:将改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水,改性分子筛复合柔性陶瓷纳米纤维材料通过臭氧催化氧化法1h内对苯甲酸钠的降解率达到100%,通过过硫酸盐氧化法1h内对苯酚的降解率达到100%;测试方法如实施例1。
实施例8
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为50wt%的钛酸异丙酯、含量为7wt%的聚乙烯醇缩丁醛和正丙醇组成;
静电纺丝的参数为:相对湿度35%,温度35℃,电压30kV,灌注速度6mL/h,纺丝距离26cm,滚筒速度60r/min,滑台运行速度50cm/min;
(2)将分子筛(钛硅分子筛TS-1)分散在水中,制得浓度为38wt%的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(1)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度35%,温度35℃,电压22kV,灌注速度7mL/h,喷涂距离26cm,滚筒速度55r/min,滑台运行速度40cm/min;
(3)在步骤(2)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(1)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度800℃,升温速率7℃/min,保温时间4h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化钛纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的分子筛;柔性陶瓷纳米纤维膜的比表面积为176m2/g,厚度为80μm,纤维直径为400~500nm。
应用:改性分子筛复合柔性陶瓷纳米纤维材料用于氮氧分离。
实施例9
一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,具体步骤如下:
(1)由前驱体溶液经静电纺丝制得杂化纳米纤维膜;
前驱体溶液由含量为30wt%的质量比为1:1的正硅酸乙酯和硅酸钠的混合物、含量为10wt%的聚氧化乙烯和质量比为1:1的丙二醇和仲丁醇混合物组成;
静电纺丝的参数为:相对湿度35%,温度26℃,电压25kV,灌注速度1mL/h,纺丝距离16cm,滚筒速度20r/min,滑台运行速度30cm/min;
(2)将分子筛(ZSM-5分子筛)分散在N,N-二甲基甲酰胺中,制得浓度为32wt%的分子筛分散液,利用静电纺丝装置将其喷涂于步骤(1)所得杂化纳米纤维膜上;
喷涂的参数为:相对湿度35%,温度26℃,电压20kV,灌注速度5mL/h,喷涂距离16cm,滚筒速度20r/min,滑台运行速度20cm/min;
(3)在步骤(2)所得材料上,在喷涂分子筛分散液的那一面,重复步骤(1)后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
煅烧的参数为:煅烧温度700℃,升温速率6℃/min,保温时间3h。
制得的改性分子筛复合柔性陶瓷纳米纤维材料,包含2层柔性二氧化硅纳米纤维膜(由杂化纳米纤维膜经过煅烧处理制得)以及封装于相邻两层柔性陶瓷纳米纤维膜之间的分子筛;柔性陶瓷纳米纤维膜的比表面积为183m2/g,厚度为35μm,纤维直径为100~200nm。
应用:改性分子筛复合柔性陶瓷纳米纤维材料用于氮氧分离。
Claims (6)
1.一种改性分子筛复合柔性陶瓷纳米纤维材料,其特征在于,包含两层以上柔性陶瓷纳米纤维膜以及封装于相邻两层柔性陶瓷纳米纤维膜之间的分子筛;
柔性陶瓷纳米纤维膜的比表面积为40~200m²/g,厚度为10~100μm,纤维直径为100~600nm;改性分子筛复合柔性陶瓷纳米纤维材料中分子筛的含量为20~90wt%;
分子筛上还负载有活性组分;活性组分在分子筛上的负载量为3~65wt%;
改性分子筛复合柔性陶瓷纳米纤维材料用于催化氧化降解工业废水。
2.根据权利要求1所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,其特征在于,柔性陶瓷纳米纤维膜为柔性二氧化硅纳米纤维膜或柔性二氧化钛纳米纤维膜。
3.根据权利要求1所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,其特征在于,活性组分为金属氧化物;负载有活性组分的分子筛是通过将分子筛浸渍于金属盐溶液中后进行干燥和焙烧获得的;金属盐溶液中金属元素的含量为分子筛重量的5~80wt%;分子筛与金属盐溶液的质量比为1:10~100;浸渍时间为10~360min,温度为20~80℃。
4.根据权利要求3所述的一种改性分子筛复合柔性陶瓷纳米纤维材料,其特征在于,金属盐为硝酸铁、硫酸亚铁、硝酸锰、氯化锰、硝酸铜和硝酸钴中的一种以上;金属盐溶液中的溶剂为水和/或乙醇。
5.制备如权利要求1~4任一项所述的一种改性分子筛复合柔性陶瓷纳米纤维材料的方法,其特征在于,在同一接收基材上先后交替进行杂化纳米纤维膜的沉积和分子筛分散液的喷涂,并控制沉积次数比喷涂次数多一次后,进行煅烧处理制得改性分子筛复合柔性陶瓷纳米纤维材料;
杂化纳米纤维膜由前驱体溶液经静电纺丝制得,前驱体溶液包含陶瓷前驱体、高分子聚合物和溶剂。
6.根据权利要求5所述的方法,其特征在于,陶瓷前驱体为正硅酸乙酯、硅酸钠、六甲基二氧硅烷、钛酸四丁酯、钛酸异丙酯和钛酸四乙酯中的一种以上;
高分子聚合物为聚已烯醇、聚乙烯吡咯烷酮、聚氧化乙烯和聚乙烯醇缩丁醛中的一种以上;
前驱体溶液中的溶剂为水、冰乙酸、甲醇、乙醇、正丙醇、正丁醇、乙二醇、丙二醇、仲丁醇和N,N-二甲基甲酰胺中的一种以上;
前驱体溶液中,陶瓷前驱体的含量为10~50wt%,高分子聚合物的含量为1~10wt%;
静电纺丝的参数为:相对湿度25~55%,温度18~35℃,电压5~30kV,灌注速度0.1~10mL/h,纺丝距离10~40cm,滚筒速度5~100r/min,滑台运行速度5~100cm/min;
分子筛分散液中的溶剂为水、冰乙酸、乙醇和N,N-二甲基甲酰胺中的一种以上;分子筛分散液的浓度为10~50wt%;
喷涂采用静电纺丝装置;喷涂的参数为:相对湿度25~55%,温度18~35℃,电压10~30kV,灌注速度0.1~10mL/h,喷涂距离10~40cm,滚筒速度5~80r/min,滑台运行速度5~100cm/min;
煅烧的参数为:煅烧温度400~1000℃,升温速率2~10℃/min,保温时间0~6h。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110443629.3A CN113171800B (zh) | 2021-04-23 | 2021-04-23 | 改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110443629.3A CN113171800B (zh) | 2021-04-23 | 2021-04-23 | 改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113171800A CN113171800A (zh) | 2021-07-27 |
CN113171800B true CN113171800B (zh) | 2022-08-23 |
Family
ID=76924552
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110443629.3A Active CN113171800B (zh) | 2021-04-23 | 2021-04-23 | 改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113171800B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114797762B (zh) * | 2022-04-18 | 2023-07-18 | 广州滨横低碳科技有限公司 | 一种改性分子筛、其制备方法及在高炉鼓风除湿中的应用 |
CN116813368A (zh) * | 2023-06-08 | 2023-09-29 | 东华大学 | 弹性层状结构二氧化钛陶瓷纳米纤维体型材料的制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106278368A (zh) * | 2016-08-15 | 2017-01-04 | 北京大学深圳研究生院 | 一种复合分子筛膜及其制备方法和应用 |
CN109894143A (zh) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | 一种用于类芬顿处理的分子筛催化剂的制备方法 |
CN111995798B (zh) * | 2018-06-18 | 2022-04-15 | 杭州沸创生命科技股份有限公司 | 一种包含分子筛和纤维的复合材料、其制备方法和用途 |
CN110205817A (zh) * | 2019-06-12 | 2019-09-06 | 东华大学 | 一种柔性透明SiO2陶瓷薄膜的制备方法 |
-
2021
- 2021-04-23 CN CN202110443629.3A patent/CN113171800B/zh active Active
Also Published As
Publication number | Publication date |
---|---|
CN113171800A (zh) | 2021-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113171800B (zh) | 改性分子筛复合柔性陶瓷纳米纤维材料及其制法和应用 | |
CN107159130B (zh) | 一种金属-有机骨架纤维膜的制备方法 | |
US9023207B2 (en) | Spiral wound carbon membrane and preparation method thereof | |
CN100384722C (zh) | 一种纳米杂化炭膜的制备方法 | |
CN101068958A (zh) | 功能性多孔多层纤维及其制备 | |
CN109876668B (zh) | 一种凹凸棒石基的陶瓷微滤膜制膜液 | |
CN108404987B (zh) | 一种提高纳米颗粒@MOFs材料催化效率的方法 | |
WO2016057361A1 (en) | Non-extruded activated carbon honeycomb structures | |
CN107376888B (zh) | 一种柔性氧化钛/氧化硅/碳复合纳米纤维膜及其制备方法 | |
CN102068915A (zh) | 一种双层中空纤维混合基质膜及其制备方法 | |
CN113912069A (zh) | 催化用纳米二氧化硅溶胶颗粒的制备方法 | |
CN114570436A (zh) | 一种高效稳定多层次分子筛中空纤维催化膜的制备方法 | |
CN108815954B (zh) | 一种纤维素/聚酰胺防静电空气净化复合膜及制备方法 | |
CN113308753A (zh) | 一种高温可吸附的多孔聚酰亚胺纳米纤维及其制备方法和应用 | |
CN109675559B (zh) | 抗劣化的挥发性有机物净化的催化剂及其制备方法 | |
CN111672330A (zh) | 一种采用热退火后合成技术制备mof纳滤膜的方法 | |
CN109876775B (zh) | 一种金属有机骨架纤维材料及其制备方法 | |
CN114480321B (zh) | 磁性Zr-MOF@PVP@Fe3O4固定化酶反应器及其应用 | |
CN114643077B (zh) | 一种具有光催化活性的微孔胶聚体及其制备方法 | |
CN115644174A (zh) | 一种银/石墨炔复合材料及其制备方法和应用 | |
CN114381829B (zh) | 利用聚丙烯腈制备高选择性分离多种小分子气体的微孔碳纤维材料及其制备方法与用途 | |
CN106474945A (zh) | 一种抗菌聚酰胺高分子膜及其制备方法和应用 | |
WO2022246214A1 (en) | Additive manufacturing techniques and ink formulations for incorporating adsorbent particles | |
CN114425406A (zh) | 用于择形催化沸石分子筛催化剂的SiO2定向修饰方法 | |
CN117599834B (zh) | 一种光催化纳米纤维膜及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |