CN108295862A - 一种用于染料废水处理的片状钼酸铁光催化剂及制备方法 - Google Patents
一种用于染料废水处理的片状钼酸铁光催化剂及制备方法 Download PDFInfo
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- CN108295862A CN108295862A CN201810163420.XA CN201810163420A CN108295862A CN 108295862 A CN108295862 A CN 108295862A CN 201810163420 A CN201810163420 A CN 201810163420A CN 108295862 A CN108295862 A CN 108295862A
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- photochemical catalyst
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- sheet iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 60
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 21
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229960002413 ferric citrate Drugs 0.000 claims abstract description 19
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims abstract description 19
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 19
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 19
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011240 wet gel Substances 0.000 claims abstract description 19
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- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910000519 Ferrosilicon Inorganic materials 0.000 claims description 4
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- 108010073385 Fibrin Proteins 0.000 claims description 4
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052571 earthenware Inorganic materials 0.000 claims 1
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 12
- 229960000907 methylthioninium chloride Drugs 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
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- 239000013078 crystal Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
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- 239000011790 ferrous sulphate Substances 0.000 description 1
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- 238000007667 floating Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
本发明涉及废水处理领域,公开了一种用于染料废水处理的片状钼酸铁光催化剂及制备方法。包括如下制备过程:(1)将各原料按照以下质量份制得混合反应液:柠檬酸铁铵24~28份、钼酸钠30~34份、去离子水30~41份、蛋白质5~8份;(2)将混合反应液中调节pH值至4~8后水浴加热,制得湿凝胶;(3)加热烘干得到干凝胶;(4)将干凝胶加热至600~800℃处理2~3h,研磨制得用于染料废水处理的片状钼酸铁光催化剂。本发明制得的钼酸铁光催化剂与普通钼酸盐光催化剂相比,比表面积大,分散性好,太阳光利用率高,量子效率高,光催化活性极强,性能稳定,可快速有效降解印染废水中污染物。
Description
技术领域
本发明涉及废水处理领域,公开了一种用于染料废水处理的片状钼酸铁光催化剂及制备方法。
背景技术
印染行业是工业废水排放大户,印染废水具有水量大、有机污染物含量高、色度深、碱性大、水质变化大等特点,属难处理的工业废水。近年来由于化学纤维织物的发展,仿真丝的兴起和印染后整理技术的进步,使浆料、人造丝碱解物、新型助剂等难生化降解有机物大量进入印染废水,传统的化学沉淀和气浮法对这类印染废水脱色效果率也非常有限。因此开发经济有效实用的印染废水处理技术已成为当今环保行业关注的重点。
在废水处理技术中,光催化氧化法是建立在能带理论的基础上,以n型半导体作敏化剂的一种光敏氧化法。光催化技术以其易操作、无污染、可直接利用太阳光等优点成为当前太阳能利用的研究热点之一。基于半导体材料的光催化技术在净化水污染、有机合成和光解水制氢等环境与资源的利用方面具有重要的应用,是一种高效、低能耗、洁净、无二次污染的技术。
影响光催化技术的关键是催化剂的选择,常用的半导体催化剂有二氧化钛、硫化镉、氧化锌、三氧化二铁等,近年来,钼酸盐作为多金属氧酸盐的一个分支,由于具有高比表面和表面能、多活性点、高选择性而受到人们的广泛关注,在光致发光和催化方面受到广泛关注,特别是金属钼酸盐作为烃类选择氧化反应的催化剂已取得一定进展。
中国发明专利申请号201110347429.4公开了一种具有片层结构的钼酸铁纳米锥材料的制备方法,其以钼酸铵和硫酸亚铁为反应原料,以乙二胺四乙酸(EDTA)为配位剂,蒸馏水为溶剂,采用微波辐射法来制备由纳米片结构组装成的钼酸铁纳米锥材料。这种钼酸铁纳米锥材料是厚度为20~40纳米的纳米片层结构组装而成、其长度为5-15微米。该工艺操作简便、实验条件可控性强、适合连续操作环境下的批量可控生产;明显优点和有益效果体现在此配位剂辅助微波辐射技术实现了对初期城和速率的有效控制,从而降低了晶体生长的速率,最终得到了形貌规整的钼酸铁一维纳米材料,材料可应用于光学、电学、催化及传感等重要领域。
中国发明专利申请号201710315937.1公开了一种高活性、晶面暴露的单斜晶型钼酸铁纳米片的制备方法,该钼酸铁纳米片的高活性晶面为暴露的(100)面,其使得该钼酸铁纳米片比一般纳米钼酸铁具有更高的催化活性。制备时,首先将硝酸铁水溶液和钼酸钠水溶液混合后调节pH至0.6~1.0,再加入晶面控制剂硝酸钠或氟化钠,加热混合溶液进行水热反应,分离即得。分析测试结果表明,该钼酸铁纳米片催化甲醇转化为甲醛的选择率大于96%,转化率大于92%。
根据上述,现有方案中的钼酸盐类光催化剂比表面积小,分散性差,性能稳定性差,催化活性低,对污水中污染物的催化降解效果差,本发明提出了一种用于染料废水处理的片状钼酸铁光催化剂及制备方法,可有效解决上述技术问题。
发明内容
目前应用较广的钼酸盐类光催化剂,特别是钼酸铁催化剂存在比表面积小,分散性差,性能稳定性差,催化活性低,对污水中污染物的催化降解效果差等问题。
为解决上述问题,本发明采用以下技术方案:
一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,制备的具体过程为:
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至4~8,然后置于水浴中加热至80~90℃,反应7~10h,制得湿凝胶;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至600~800℃处理2~3h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂。
优选的,步骤(1)所述蛋白质为纤维蛋白、球蛋白、胶原蛋白、伴娘蛋白中的至少一种。
优选的,步骤(1)所述混合反应液中,按重量份计,其中:柠檬酸铁铵24~28份、钼酸钠30~34份、去离子水30~41份、蛋白质5~8份。
优选的,步骤(1)所述搅拌器为涡轮式搅拌器、旋浆式搅拌器、螺带式搅拌器、折叶式搅拌器中的一种,搅拌速度为800~1100r/min,搅拌时间为60~80min。
优选的,步骤(2)所述酸碱调节剂为碳酸钠、碳酸钾、柠檬酸、乙酸、乳酸中的至少一种。
优选的,步骤(3)所述烘干的加热温度为130~150℃,时间为2~3h。
优选的,步骤(4)所述坩埚为天然石墨坩埚、耐火黏土坩埚、硬质高岭土坩埚、碳化硅坩埚、氧化铝金刚砂坩埚、硅铁坩埚中的一种。
优选的,步骤(4)所述研磨采用三辊研磨机,研磨后的钼酸铁催化剂的粒径为50~100μm。
由上述方法制备得到的一种用于染料废水处理的片状钼酸铁光催化剂,利用蛋白质具有快速吸附到界面的能力,所以当其达到界面后可迅速伸展和取向,使得制备的片状钼酸铁光催化剂光催化剂具有比表面积大、分散性好,性能稳定的优点,光催化活性极高,可快速有效降解染料废水中的污染物。
测试本发明制备的钼酸铁光催化剂的比表面积、分散特征、太阳光利用率及亚甲基蓝降解率,并与普通颗粒状钼酸铁光催化剂及颗粒状二氧化钛光催化剂相对比,本发明的方法具有明显优势,如表1所示。
表1:
性能指标 | 本发明 | 普通颗粒状钼酸铁光催化剂 | 颗粒状二氧化钛光催化剂 |
比表面积(m2/g) | 260~300 | 180~220 | 200~250 |
分散特征 | 均匀分布 | 有团聚现象 | 有团聚现象 |
太阳光利用率(%) | 20~25 | 15~19 | 13~17 |
亚甲基蓝降解率(%) | 90~95 | 70~78 | 72~79 |
本发明提供了一种用于染料废水处理的片状钼酸铁光催化剂及制备方法,与现有技术相比,其突出的特点和优异的效果在于:
1、提出了采用钼酸盐干凝胶制备用于染料废水处理的片状钼酸铁光催化剂的方法。
2、利用蛋白质具有快速吸附到界面的能力,当其达到界面后可迅速伸展和取向的特性,制得的片状钼酸铁光催化剂具有比表面积大,分散性好,太阳光利用率高。
3、本发明制备得到的光催化剂量子效率高,光催化活性极强,性能稳定,可快速有效降解印染废水中污染物。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明,但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;蛋白质为纤维蛋白;搅拌器为涡轮式搅拌器,搅拌速度为1000r/min,搅拌时间为70min;
混合反应液中,按重量份计,其中:柠檬酸铁铵26份、钼酸钠32份、去离子水35份、蛋白质6份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至6,然后置于水浴中加热至85℃,反应8h,制得湿凝胶;酸碱调节剂为碳酸钠;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为140℃,时间为2.5h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至700℃处理2.5h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为天然石墨坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为80μm。
实施例1制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
实施例2
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;蛋白质为球蛋白;搅拌器为旋浆式搅拌器,搅拌速度为800r/min,搅拌时间为80min;
混合反应液中,按重量份计,其中:柠檬酸铁铵24份、钼酸钠30份、去离子水41份、蛋白质5份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至4,然后置于水浴中加热至80℃,反应10h,制得湿凝胶;酸碱调节剂为碳酸钾;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为130℃,时间为3h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至600℃处理3h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为耐火黏土坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为50μm。
实施例2制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
实施例3
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;蛋白质为胶原蛋白;搅拌器为螺带式搅拌器,搅拌速度为1100r/min,搅拌时间为60min;
混合反应液中,按重量份计,其中:柠檬酸铁铵28份、钼酸钠34份、去离子水30份、蛋白质8份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至8,然后置于水浴中加热至90℃,反应7h,制得湿凝胶;酸碱调节剂为柠檬酸;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为150℃,时间为2h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至800℃处理2h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为硬质高岭土坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为100μm。
实施例3制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
实施例4
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;蛋白质为伴娘蛋白;搅拌器为折叶式搅拌器,搅拌速度为900r/min,搅拌时间为75min;
混合反应液中,按重量份计,其中:柠檬酸铁铵25份、钼酸钠31份、去离子水38份、蛋白质6份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至5,然后置于水浴中加热至82℃,反应8h,制得湿凝胶;酸碱调节剂为乙酸;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为135℃,时间为2h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至650℃处理3h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为碳化硅坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为60μm。
实施例4制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
实施例5
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;蛋白质为纤维蛋白;搅拌器为涡轮式搅拌器,搅拌速度为1000r/min,搅拌时间为75min;
混合反应液中,按重量份计,其中:柠檬酸铁铵27份、钼酸钠33份、去离子水33份、蛋白质7份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至7,然后置于水浴中加热至88℃,反应8h,制得湿凝胶;酸碱调节剂为乳酸;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为145℃,时间为3h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至750℃处理2h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为氧化铝金刚砂坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为90μm。
实施例5制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
实施例6
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;蛋白质为球蛋白;搅拌器为旋浆式搅拌器,搅拌速度为900r/min,搅拌时间为75min;
混合反应液中,按重量份计,其中:柠檬酸铁铵26份、钼酸钠33份、去离子水35份、蛋白质6份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至5,然后置于水浴中加热至86℃,反应8h,制得湿凝胶;酸碱调节剂为碳酸钠;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为145℃,时间为3h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至750℃处理3h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为硅铁坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为80μm。
实施例6制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
对比例1
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;搅拌器为旋浆式搅拌器,搅拌速度为900r/min,搅拌时间为75min;
混合反应液中,按重量份计,其中:柠檬酸铁铵26份、钼酸钠33份、去离子水41份;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至5,然后置于水浴中加热至86℃,反应8h,制得湿凝胶;酸碱调节剂为碳酸钠;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;烘干的加热温度为145℃,时间为3h;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至750℃处理3h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂;坩埚为硅铁坩埚;研磨采用三辊研磨机,研磨后的钼酸铁催化剂的平均粒径为80μm。
对比例1在混合反应液制备中未加入蛋白质,制得的钼酸铁光催化剂,其比表面积、分散特征、太阳光利用率及亚甲基蓝降解率如表2所示。
上述性能指标的测试方法为:
采用比表面积测试仪测定本发明制得的光催化剂的比表面积;
采用电子显微镜观察本发明制得的光催化剂在废水中的分散特征,表征其分散性;
采用太阳光照射制得的光催化剂,测得材料可吸收的可见光的波长范围W1,太阳光波长总范围为W,以W1/W×100%计算得到材料的太阳光利用率;
将本发明制得的光催化剂投入一定量的亚甲基蓝废水中,在20℃下采用太阳光照射下,分别测定试验开始以及5h后亚甲基蓝的含量,计算得到亚甲基蓝的降解率,表征其光催化降解效果。
表2:
性能指标 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 实施例6 | 对比例1 |
比表面积(m2/g) | 277 | 287 | 285 | 295 | 286 | 294 | 204 |
分散特征 | 均匀分布 | 均匀分布 | 均匀分布 | 均匀分布 | 均匀分布 | 均匀分布 | 有团聚现象 |
太阳光利用率(%) | 22.5 | 23.4 | 22.8 | 23.4 | 24.2 | 24.1 | 19.5 |
亚甲基蓝降解率(%) | 92.2 | 93.3 | 92.4 | 93.1 | 94.2 | 93.8 | 80.3 |
Claims (9)
1.一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于,制备的具体过程为:
(1)先将柠檬酸铁铵加入去离子水中配成水溶液,然后加入蛋白质,置于搅拌器中搅拌溶解,并在搅拌状态下加入钼酸钠,混合均匀,制得混合反应液;
(2)先向步骤(1)制得的混合反应液中滴加酸碱调节剂,调节pH值至4~8,然后置于水浴中加热至80~90℃,反应7~10h,制得湿凝胶;
(3)将步骤(2)制得的湿凝胶进行加热烘干,得到干凝胶;
(4)将步骤(3)得到的干凝胶转移到坩埚中,加热至600~800℃处理2~3h,然后进行研磨,制得用于染料废水处理的片状钼酸铁光催化剂。
2.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(1)所述蛋白质为纤维蛋白、球蛋白、胶原蛋白、伴娘蛋白中的至少一种。
3.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(1)所述混合反应液中,按重量份计,其中:柠檬酸铁铵24~28份、钼酸钠30~34份、去离子水30~41份、蛋白质5~8份。
4.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(1)所述搅拌器为涡轮式搅拌器、旋浆式搅拌器、螺带式搅拌器、折叶式搅拌器中的一种,搅拌速度为800~1100r/min,搅拌时间为60~80min。
5.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(2)所述酸碱调节剂为碳酸钠、碳酸钾、柠檬酸、乙酸、乳酸中的至少一种。
6.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(3)所述烘干的加热温度为130~150℃,时间为2~3h。
7.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(4)所述坩埚为天然石墨坩埚、耐火黏土坩埚、硬质高岭土坩埚、碳化硅坩埚、氧化铝金刚砂坩埚、硅铁坩埚中的一种。
8.根据权利要求1所述一种用于染料废水处理的片状钼酸铁光催化剂的制备方法,其特征在于:步骤(4)所述研磨采用三辊研磨机,研磨后的钼酸铁催化剂的粒径为50~100μm。
9.权利要求1~8任一项所述方法制备得到的一种用于染料废水处理的片状钼酸铁光催化剂。
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CN111659411A (zh) * | 2020-07-10 | 2020-09-15 | 西北师范大学 | 一种稀土铈掺杂钼酸铁光催化剂的制备及应用 |
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CN110893344B (zh) * | 2018-09-13 | 2021-04-27 | 中国科学院大连化学物理研究所 | 一种甲醇氧化制甲醛铁钼催化剂及制备和应用 |
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