CN116139921B - 尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用 - Google Patents
尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用 Download PDFInfo
- Publication number
- CN116139921B CN116139921B CN202310447874.0A CN202310447874A CN116139921B CN 116139921 B CN116139921 B CN 116139921B CN 202310447874 A CN202310447874 A CN 202310447874A CN 116139921 B CN116139921 B CN 116139921B
- Authority
- CN
- China
- Prior art keywords
- tail coal
- tio
- cds
- composite photocatalyst
- based zeolite
- 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
- 239000003245 coal Substances 0.000 title claims abstract description 127
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 67
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title description 17
- 239000010457 zeolite Substances 0.000 title description 17
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000725 suspension Substances 0.000 claims abstract description 26
- 238000011282 treatment Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000002910 solid waste Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000004108 freeze drying Methods 0.000 description 12
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- -1 silicate ions Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000005188 flotation Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011847 coal-based material Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7053—A-type
-
- B01J35/23—
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
-
- 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
-
- 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
本发明提出了尾煤基沸石@CDs‑TiO2复合光催化剂的制备方法及应用,属于固体废弃物利用技术领域;是先将尾煤经过酸化处理和高温焙烧得到改性尾煤粉,然后将改性尾煤粉、TiO2加入碱液中得到混合悬浊液;将混合悬浊液在紫外光辐照条件下搅拌老化,将老化处理后的混合悬浊液进行水热反应,再经过滤洗涤干燥制得;所述尾煤基沸石@CDs‑TiO2复合光催化剂用于催化降解亚甲基蓝;本发明利用尾煤制备催化剂来处理水中的有机污染物,具有响应波长红移、光催化活性高的优点,可应用于环保领域。
Description
技术领域
本发明属于固体废弃物利用技术领域,涉及对含碳类矿物尾煤的利用,具体为一种尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用,适用于可见光下对亚甲基蓝的催化降解。
背景技术
1977年,FRANK和BARD利用二氧化钛,在紫外光照射下,降解水中的氰化物,使光催化技术用于污水处理成为可能。利用半导体光催化技术降解有机污染物因节能、高效越来越引起了人们广泛的关注。在光催化剂中,锐钛矿型二氧化钛因其成本相对较低、优越的光催化性能、长期稳定性和环境友好性,是最有前途的催化剂之一,研究人员普遍认为:(1)锐钛矿的禁带宽度为3.2eV;(2)锐钛矿表面吸附H2O、O2以及OH-能力较强,被大于禁带宽度能量的光量子激发后,其表面聚积较多的O2 -·(导带)和OH·(价带)自由基创造了强力氧化环境。
在工业固体废弃物中,煤基固体废弃物产量占比最高,煤基固体废弃物主要指矿井生产过程中产生的热值低、含碳的类石矿物,如煤矸石和煤炭尾矿,以及燃煤电厂排放的粉煤灰,这些固废排放量呈逐年上升趋势,产生了一系列生态环境问题。将这些含碳的类石材料制备为高价值新材料是有效的环保途径和研究热点。
碳点(CDs),一种新型的纳米碳,由于其独特性,吸引越来越多的关注。如其独特的上转换发光和尺寸依赖的光致发光特性、化学惰性、优越的抗光腐蚀性,优异的水溶解度,以及低细胞毒性。越来越多的研究开始关注将碳点与二氧化钛进行耦合,CDs的共轭sp2结构对提高其光催化活性起着重要作用,如,促进电子空穴对的激发和分离。CDs的合成一般可以分为“自上而下”和“自下而上”两种方法;“自上而下”的方法是通过宏观的碳结构合成CDs,如煤、石墨、活性炭和碳黑;强酸氧化是从煤基材料中提取碳点对的一种有效、方便的“自上而下”的方法,但强酸氧化要求剧烈的氧化环境用以将宏观煤质碳结构剥离剪切为碳点,故传统强酸氧化存在产生二次污染的问题。
在紫外光激发下,由二氧化钛产生的O2 -·和OH·同样可以为碳点剥离创造绿色的强氧化环境,这为紫外辅助合成碳点提供基础。另一方面,沸石分子筛大多数是在强碱性的介质中通过硅酸根离子及硅铝酸根离子的解聚和缩聚重排而形成的。向沸石反应溶液引入二氧化钛后,通过紫外辐射二氧化钛表面产生大量的羟基自由基,可以促进硅酸根离子及硅铝酸根离子的解聚和缩聚,从而显著加速了沸石分子筛的晶化过程,并降低制备所需碱度,缩短沸石合成所需的时间。
发明内容
本发明克服了现有技术的不足,提出一种尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用。解决当前存在的煤基固体废弃物堆存造成的空间浪费和环境污染问题,以及现有的粉末光催化剂可见光利用率低,尤其是回收利用难度大的问题。
为了达到上述目的,本发明是通过如下技术方案实现的。
尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,包括以下步骤:
1)尾煤预处理:将尾煤粉浸入酸液中充分搅拌进行酸化处理,之后在惰性气体保护下,将酸化处理后的尾煤粉在700-900℃下焙烧并保温处理,得到改性尾煤粉;
2)将TiO2加入碱液中,再加入所述的改性尾煤粉进行搅拌得到混合悬浊液;TiO2与改性尾煤粉的质量比为0.5-1;然后将混合悬浊液在紫外光辐照条件下搅拌老化8-16h,光照强度为10-20mW/cm2;
3)将老化处理后的混合悬浊液进行水热反应,得到的产物经过滤洗涤干燥得到尾煤基沸石@CDs-TiO2复合光催化剂。
所述的尾煤是煤基固体废弃物,是指矿井生产过程中产生的热值低、含碳的类石矿物,如煤矸石和煤炭尾矿。
优选的,所述尾煤粉的粒径<125μm。
优选的,所述的酸化处理是将尾煤粉置于0.1M的稀盐酸中超声处理1.5-2.5h。
优选的,所述的碱液为1-3M的NaOH溶液。
优选的,所述水热反应的温度为115-125℃,时间为20-30h。
优选的,所述的焙烧是在管式炉中通入惰性气体,以5℃/min升温速度将酸化处理后的尾煤粉在700-900℃下焙烧并保温处理。
更优的,所述的惰性气体为N2,惰性气体的流速为100mL/min。
优选的,保温处理的时间为1h。
优选的,步骤3)所述的洗涤干燥是使用去离子水将得到的产物洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
所述制备方法制备的尾煤基沸石@CDs-TiO2复合光催化剂用于催化降解亚甲基蓝。
本发明相对于现有技术所产生的有益效果为:
本发明从尾煤固体废弃物特性、复合半导体材料光生电子和光生空穴的分离机理出发,提出了一种通过光催化氧化浮选尾煤在低碱度环境原位制备尾煤基沸石@CDs-TiO2复合光催化剂的方法,优势在于:
(1)本发明提出的尾煤基沸石@CDs-TiO2复合光催化剂,尾煤材料来源为动力煤选煤厂,价格低廉,来源广泛,制备流程便捷可靠。低值浮选尾煤用于制备复合光催化剂,得到高值化利用,以废治废。
(2)本发明以尾煤粉作为碳源、硅铝源,通过二氧化钛光响应特性在紫外光辐照下产生各类自由基反应,原位制备碳点和煤基沸石硅铝凝胶;通过水热反应和晶化反应制备尾煤基沸石@CDs-TiO2复合光催化剂。克服了TiO2单独作为光催化剂存在的问题:即光生电子空穴复合严重、量子效率低、不能有效利用太阳光等。
本方法的创新点在于,碳点可以作为电子槽和敏化剂,捕获更长波长光照下半导体激发的电子,阻碍了电子空穴对的复合;沸石有丰富孔结构,可提供更多的吸附位点,增强吸附-降解协同作用;同时,沸石的存在增强了该复合光催化剂的可回收性和重复利用性,促进了污水处理领域发展以及煤炭固废的高质化利用。
本发明制备的尾煤基沸石@CDs-TiO2复合光催化剂在更长波长的光照下对有机污染物具有比纯二氧化钛更高效的催化降解效果;通过将粉体二氧化钛催化剂颗粒负载于尾煤基沸石,有利于对光催化剂分离回收。
(3)本发明已在亚甲基蓝降解处理实例中得到验证,具有明显光催化效果,光催化活性较高,对有机物的降解率较高。本发明提供的尾煤基沸石@CDs-TiO2复合光催化剂具有响应波长红移、光催化活性高的优点,因此可以用于环保领域,主要是用于处理水中的有机污染物等,对亚甲基蓝去除率达到90.43%。
附图说明
图1为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂样品的XRD图谱。
图 2为实施例 8 制备的尾煤基沸石@CDs-TiO2复合光催化剂样品放大1000倍的扫描电镜图。
图3为实施例 8 制备的尾煤基沸石@CDs-TiO2复合光催化剂样品放大35000倍的扫描电镜图。
图4为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂样品的BET氮气吸附图。
图5为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂样品的孔径分布图。
图6为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂的Raman光谱图。
图7为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂的UV-vis光谱图。
图8为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂和纯锐钛矿二氧化钛样品在可见光照射下光催化降解10mg/L亚甲基蓝的比较图。
图9为实施例8制备的尾煤基沸石@CDs-TiO2复合光催化剂和纯锐钛矿二氧化钛样品回收性循环光催化实验结果的比较图。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白,结合实施例和附图,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。下面结合实施例及附图详细说明本发明的技术方案,但保护范围不被此限制。
实施例1
一种尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,具体为以下步骤:
步骤1:尾煤预处理:将已破碎至125μm以下的尾煤粉在0.1M稀盐酸中超声2h;将混合液进行抽滤并用去离子水反复冲洗底物,冷冻干燥;再在管式炉中通入N2,流速控制在100mL/min,以5℃/min升温速度将底物在800℃条件下保温1h,得到深灰色改性尾煤粉。
步骤2:将1.0g的TiO2加入2M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉(即,TiO2与改性尾煤粉质量比为0.5)继续搅拌15min得到混合悬浊液;然后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化16h,光照强度为10mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为120℃,时间为24h);水热反应得到的产物经过离心过滤掉上清液,使用去离子水将离心得到的固体物洗至中性,冷冻干燥48h后,得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例2
步骤1:尾煤预处理:将已破碎至125μm以下的尾煤粉在0.2M稀盐酸中超声2.5h;将混合液进行抽滤并用去离子水反复冲洗底物,冷冻干燥;再在管式炉中通入N2,流速控制在120mL/min,以6℃/min升温速度将底物在900℃条件下保温1.5h,得到深灰色改性尾煤粉。
步骤2:将2.0g的TiO2加入2M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉(即,TiO2与改性尾煤粉质量比为1)继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化8h,光照强度为10mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为115℃,时间为30h);得到的产物经过离心过滤掉上清液,使用去离子水将离心后的固体物洗至中性,冷冻干燥40h后得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例3
步骤1:尾煤预处理:将已破碎至125μm以下的尾煤粉在0.2M稀盐酸中超声1.5h;将混合液进行抽滤并用去离子水反复冲洗底物,冷冻干燥;再在管式炉中通入N2,流速控制在90mL/min,以6℃/min升温速度将底物在700℃条件下保温1.5h,得到深灰色改性尾煤粉。
步骤2:将2.0g的TiO2加入1M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉(即,TiO2与改性尾煤粉质量比为1)继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化16h,光照强度为12mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为120℃,时间为24h);得到的产物经过离心过滤掉上清液,使用去离子将离心得到的固体物水洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例4
步骤1:按实施例1进行尾煤预处理。
步骤2:将2.0g的TiO2加入3M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉(即,TiO2与改性尾煤粉质量比为1)继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化16h,光照强度为16mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为120℃,时间为24h);得到的产物经过离心过滤掉上清液,使用去离子水将离心得到的固体物洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例5
步骤1:按实施例1进行尾煤预处理。
步骤2:将2.0g的TiO2加入2M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉,继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化8h,光照强度为18mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为125℃,时间为30h);得到的产物经过离心过滤掉上清液,使用去离子将离心得到的固体物水洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例6
步骤1:按实施例1进行尾煤预处理。
步骤2:将1.5g的TiO2加入2M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉,继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化12h,光照强度为20mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为120℃,时间为24h);得到的产物经过离心过滤掉上清液,使用去离子将离心得到的固体物水洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例7
步骤1:按实施例1进行尾煤预处理。
步骤2:将1.6g的TiO2加入2M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉,继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化10h,光照强度为20mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为125℃,时间为20h);得到的产物经过离心过滤掉上清液,使用去离子将离心得到的固体物水洗至中性,冷冻干燥40h得到尾煤基沸石@CDs-TiO2复合光催化剂。
实施例8
步骤1:按实施例1进行尾煤预处理。
步骤2:将2.0g的TiO2加入2M的NaOH溶液中,搅拌均匀后,加入2.0g步骤1制得的改性尾煤粉,继续搅拌15min得到混合悬浊液;后将混合悬浊液置于透明高硼硅管中,在紫外光辐照条件下搅拌老化16h,光照强度为20mW/cm2;再转移到水热反应釜中进行水热反应(水热反应的温度为120℃,时间为24h);得到的产物经过离心过滤掉上清液,使用去离子将离心得到的固体物水洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
以上,仅为本发明的较佳实施例,并非仅限于本发明的实施范围,凡依本发明范围的内容所做的等效变化和修饰,都应为本发明的技术范畴。
图1为所制得的实施例8煤基沸石@CDs-TiO2复合光催化剂样品的XRD图谱,由图1可以看出在2θ=24.3°附近存在微弱的衍射峰,归属于共轭sp2碳结构,说明碳点合成成功,但含量很低;同时,二氧化钛为锐钛矿型,所制的煤基沸石为4A型沸石,含量均很高且结晶度高。
图2和图3为所制得的实施例8尾煤基沸石@CDs-TiO2复合光催化剂样品在不同倍数下的扫描电镜图,由图2和图3可以看出,产物中有立方状的4A沸石分子筛生成,表面负载大量二氧化钛纳米颗粒。
图4为所制得的实施例8尾煤基沸石@CDs-TiO2复合光催化剂样品的静态氮吸脱附等温线;图5为所制得的实施例8尾煤基沸石@CDs-TiO2复合光催化剂样品的DFT孔径分布图。由图4可以看出,N2等温吸附曲线为Ⅳ型,对应于其介孔特征。另外,吸附曲线和脱附曲线在相对压强0.4至0.9处有一面积较大的滞回环,可能与氮气在部分开口、中空煤基沸石的冷凝有关;由图5的DFT孔径分布图看出,尾煤基沸石@CDs-TiO2复合光催化剂的孔径分布较窄且集中,进一步证实了合成煤基沸石@CDs-TiO2复合光催化剂结构均一性。
图6为所制得的实施例8尾煤基沸石@CDs-TiO2复合光催化剂的Raman光谱图,由图6可以看出1336cm-1和1586cm-1处分别出现了由碳原子的sp3杂化和sp2平面振动引起的D带和G带,这证明了复合光催化剂中碳点的存在;149 cm-1、394cm-1、513cm-1、637cm-1附近出现的峰是锐钛矿相TiO2的E1g、B1g、A1g、Eg带。
图7为所制得的实施例8尾煤基沸石@CDs-TiO2复合光催化剂的UV-vis光谱图,由图7可以看出,与纯锐钛矿TiO2相比,尾煤基沸石@CDs-TiO2复合光催化剂表现出光响应波长红移和可见光光吸收增加。
图8为实施例8所制的尾煤基沸石@CDs-TiO2复合光催化剂样品和纯锐钛矿二氧化钛样品在可见光照射下光催化降解10mg/L亚甲基蓝的对比图,由图8可以看出,相较于纯二氧化钛,尾煤基沸石@CDs-TiO2复合光催化剂对于10mg/L的亚甲基蓝降解效率更高,达到了90.43%;同时,在避光吸附过程中具有更强的吸附效率,表明该复合光催化剂有较强的吸附-降解协同效应。
图9为实施例8所制的尾煤基沸石@CDs-TiO2复合光催化剂样品和纯锐钛矿二氧化钛样品回收性进行的循环光催化实验的对比图,由图9可以看出,相较于纯二氧化钛,尾煤基沸石@CDs-TiO2复合光催化剂回收性明显更优,证明其优良的重复利用性。
以上内容是结合具体的优选实施方式对本发明所做的进一步详细说明,不能认定本发明的具体实施方式仅限于此,对于本发明所属技术领域的普通技术人员来说,在不脱离本发明的前提下,还可以做出若干简单的推演或替换,都应当视为属于本发明由所提交的权利要求书确定专利保护范围。
Claims (7)
1.尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,其特征在于,包括以下步骤:
1)尾煤预处理:将尾煤粉浸入酸液中充分搅拌进行酸化处理,之后在N2的保护下,将酸化处理后的尾煤粉在700-900℃下焙烧并保温处理,得到改性尾煤粉;所述的酸化处理是将尾煤粉置于0.1M的稀盐酸中超声处理1.5-2.5h;
2)将TiO2加入碱液中,再加入所述的改性尾煤粉进行搅拌得到混合悬浊液;TiO2与改性尾煤粉的质量比为0.5-1;然后将混合悬浊液在紫外光辐照条件下搅拌老化8-16h,光照强度为10-20mW/cm2;所述的碱液为1-3M的NaOH溶液;
3)将老化处理后的混合悬浊液进行水热反应,得到的产物经过滤洗涤干燥得到尾煤基沸石@CDs-TiO2复合光催化剂;所述水热反应的温度为115-125℃,时间为20-30h。
2.根据权利要求1所述的尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,其特征在于,所述尾煤粉的粒径<125μm。
3.根据权利要求1所述的尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,其特征在于,所述的焙烧是在管式炉中通入N2,以5℃/min的升温速度将酸化处理后的尾煤粉在700-900℃下焙烧并保温处理。
4.根据权利要求3所述的尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,其特征在于,N2的流速为100mL/min。
5.根据权利要求3所述的尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,其特征在于,保温处理的时间为1h。
6.根据权利要求3所述的尾煤基沸石@CDs-TiO2复合光催化剂的制备方法,其特征在于,步骤3)所述的洗涤干燥是使用去离子水将得到的产物洗至中性,冷冻干燥48h得到尾煤基沸石@CDs-TiO2复合光催化剂。
7.尾煤基沸石@CDs-TiO2复合光催化剂的应用,其特征在于,将权利要求1-6任意一项所述制备方法制备的尾煤基沸石@CDs-TiO2复合光催化剂用于催化降解亚甲基蓝。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310447874.0A CN116139921B (zh) | 2023-04-24 | 2023-04-24 | 尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用 |
US18/466,851 US11951460B1 (en) | 2023-04-24 | 2023-09-14 | Preparation method and application of tailings-based zeolite@CDs-TiO2 composite photocatalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202310447874.0A CN116139921B (zh) | 2023-04-24 | 2023-04-24 | 尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN116139921A CN116139921A (zh) | 2023-05-23 |
CN116139921B true CN116139921B (zh) | 2023-07-04 |
Family
ID=86356776
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202310447874.0A Active CN116139921B (zh) | 2023-04-24 | 2023-04-24 | 尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用 |
Country Status (2)
Country | Link |
---|---|
US (1) | US11951460B1 (zh) |
CN (1) | CN116139921B (zh) |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100582004C (zh) * | 2008-01-08 | 2010-01-20 | 中国日用化学工业研究院 | 一种煤矸石制备高白度a型沸石的方法 |
KR101403534B1 (ko) * | 2013-05-30 | 2014-06-03 | 부경대학교 산학협력단 | 탄소양자점 제조방법 |
US10266416B2 (en) * | 2013-07-05 | 2019-04-23 | Danmarks Tekniske Universitet | Method for producing zeolites and zeotypes |
CN104119164B (zh) * | 2014-08-12 | 2016-05-18 | 许盛英 | 沸石压缩营养土的生产方法 |
FR3065650B1 (fr) * | 2017-04-28 | 2019-06-28 | IFP Energies Nouvelles | Procede de reduction photocatalytique du dioxyde de carbone mettant en œuvre un photocatalyseur sous forme de monolithe poreux |
CN108636416B (zh) * | 2018-04-28 | 2021-04-13 | 河北科技大学 | 一种ZnO/煤矸石复合光催化剂及其制备方法和应用 |
CN108686656B (zh) * | 2018-04-28 | 2021-04-13 | 河北科技大学 | 一种α-Fe2O3/煤矸石复合光催化剂及其制备方法和应用 |
US11161094B2 (en) * | 2019-05-01 | 2021-11-02 | Imam Abdulrahman Bin Faisal University | Titania-carbon dot-reduced graphene oxide composites, their make, and use |
KR102262990B1 (ko) * | 2019-07-12 | 2021-06-09 | 건국대학교 산학협력단 | 석탄비산재를 이용한 실리콘 및 제올라이트의 순차적 제조방법 |
KR20220000044A (ko) * | 2020-06-25 | 2022-01-03 | 이상일 | 폐석탄재를 이용한 복합 탈취제 제조방법 |
EP3932548A1 (fr) * | 2020-06-30 | 2022-01-05 | CY Cergy Paris Université | Photo-catalyseur à base de tio2, procédés de préparation dudit photocatalyseur et son utilisation pour dégrader une biomasse |
CN113019321A (zh) * | 2021-03-04 | 2021-06-25 | 太原理工大学 | 一种煤基颗粒及其制备方法和在过滤煤炭废水中的用途 |
CN113398980B (zh) * | 2021-06-15 | 2022-07-15 | 东北大学 | 一种粉煤灰基X沸石-TiO2复合光催化剂的制备方法 |
-
2023
- 2023-04-24 CN CN202310447874.0A patent/CN116139921B/zh active Active
- 2023-09-14 US US18/466,851 patent/US11951460B1/en active Active
Also Published As
Publication number | Publication date |
---|---|
US11951460B1 (en) | 2024-04-09 |
CN116139921A (zh) | 2023-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110743588A (zh) | 一种氮掺杂生物炭催化材料及其制备方法与应用 | |
CN102527420A (zh) | 碳酸氧铋光催化剂及其制备方法 | |
CN108993550B (zh) | 一种表面氧空位改性的溴氧铋光催化剂及其制备方法 | |
CN108722422B (zh) | 一种赤泥活化改性的方法及应用 | |
CN109174082A (zh) | 一种制备BiVO4/MnO2复合光催化氧化剂的方法 | |
CN108855131B (zh) | 一种银-镍双金属掺杂二氧化钛纳米复合材料的制备和应用 | |
CN110624594A (zh) | 一种磁性Fe3O4/ZnO/g-C3N4复合光催化剂及其制备方法 | |
Meng et al. | Heterostructured nitrogen and sulfur co-doped black TiO2/g-C3N4 photocatalyst with enhanced photocatalytic activity | |
CN110756163A (zh) | 一种纳米CoFe2O4/碳纤维毡复合材料及其制备方法和应用 | |
CN110860302A (zh) | 一种AgI/LaFeO3/g-C3N4复合光催化剂的制备方法 | |
CN113398974A (zh) | 一种Fe掺杂g-C3N4光催化剂及其制备方法和应用 | |
CN109158117B (zh) | 一种全光谱响应双掺杂氟化镧/凹凸棒石上转换复合光催化材料及其制备方法与应用 | |
CN111203258A (zh) | 一种光催化剂s-c3n4的制备方法及应用 | |
CN112973744B (zh) | 一种光电催化剂及其制备方法 | |
CN114192102A (zh) | 一种一步制备多酸改性的石墨相氮化碳材料及其应用 | |
CN109603825A (zh) | 一种埃洛石纳米管负载等离子体共振光催化剂及其制备方法 | |
CN116139921B (zh) | 尾煤基沸石@CDs-TiO2复合光催化剂的制备方法及应用 | |
CN111151278B (zh) | 一种碳点复合碳酸氧铋可见光催化剂的制备方法 | |
CN111889126A (zh) | 一种具有可见光响应的类芬顿材料的制备方法及应用 | |
Lee et al. | Synthesis and characterization of carbon-doped titania as a visible-light-sensitive photocatalyst | |
CN108927124B (zh) | 一种易回收可重复利用的纳米晶TiO2包覆空心玻璃微珠光催化剂及其制备方法 | |
CN108404948B (zh) | 一种(BiO)2CO3-BiO2-x复合光催化剂及其制备方法和应用 | |
CN106732740A (zh) | 氧化锶团簇修饰的无定型氮化碳光催化剂及其制备方法 | |
CN115069282B (zh) | 一种铋酸铜/碳酸氧铋异质结光催化剂及制备方法和应用 | |
CN103521205A (zh) | 一种制备高光催化活性核壳结构TiO2材料的方法 |
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 |