CN107519865A - 一种钨酸锰复合二氧化锰催化剂的制备方法 - Google Patents
一种钨酸锰复合二氧化锰催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- CRLHSBRULQUYOK-UHFFFAOYSA-N dioxido(dioxo)tungsten;manganese(2+) Chemical compound [Mn+2].[O-][W]([O-])(=O)=O CRLHSBRULQUYOK-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000011572 manganese Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 8
- 239000011565 manganese chloride Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000004471 Glycine Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 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 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000012286 potassium permanganate Substances 0.000 abstract description 7
- 238000001035 drying Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000000356 contaminant Substances 0.000 abstract description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract description 3
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 abstract description 2
- -1 compound manganese tungstate Chemical class 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 13
- 238000004042 decolorization Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 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 description 1
- YYYARFHFWYKNLF-UHFFFAOYSA-N 4-[(2,4-dimethylphenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonic acid Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=CC=C12 YYYARFHFWYKNLF-UHFFFAOYSA-N 0.000 description 1
- 101100493710 Caenorhabditis elegans bath-40 gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical group [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明公开了一种钨酸锰复合二氧化锰催化剂的制备方法，步骤如下：将5~10 g二氯化锰加入到50~100 mL水中配制成溶液，再向该溶液中加入5~8 g高锰酸钾及3~4 g钨酸钠，60~70℃水浴中搅拌10～50分钟，再加入2~3 g甘氨酸，将溶液转移至水热反应器中，180~260℃下，反应5~10 h，过滤得到固体，用蒸馏水洗涤3~5遍，80℃烘干，即得到一种钨酸锰复合二氧化锰催化剂。二氯化锰在水热条件下同时和钨酸钠和高锰酸钾反应，形成充分复合的钨酸锰和二氧化锰复合物，可以促进锰氧化物分散，提高污染物降解速度。
Description
技术领域
本发明涉及环境污染控制新材料领域，尤其涉及一种钨酸锰复合二氧化锰催化剂的制备方法。
背景技术
随着科技的发展，来自工农业生产中产生的毒害有机污染物严重威胁着环境和人类的健康，寻求一种新型高效的环境治理技术具有重要的意义。光催化技术因其节能、高效、污染物降解彻底、无二次污染优点，目前已成为一种具有重要应用前景的新兴环境治理技术。近年来，新型高效的可见光光催化剂的研制成为光催化技术中的一个重要研究内容，其中具有表面等离子共振效应的光催化材料，因其独特的表面物理化学性质和高效的可见光光催化性能，成为研究的热点之一。
钨酸锰是一种具有钨锰铁矿结构的重要的功能材料，在光致发光、光纤、多铁材料、光催化剂、闪烁体、湿度传感器及磁性材料等方面有着广泛的应用前景。
二氧化锰为黑色或棕色的固体，是锰最稳定的氧化物，经常出现于软锰矿及锰结核中。二氧化锰主要用途为制造干电池，如碳锌电池和碱性电池；也常在化学反应中作为催化剂。
但单独使用二氧化锰作为光催化剂效果很差，并且无法得到相应的降解速度。
发明内容
本发明的目的是为克服现有技术的不足，提供一种钨酸锰复合二氧化锰催化剂的制备方法。
本发明采用的技术方案是依次包括如下步骤：将5~10 g二氯化锰加入到50~100mL水中配制成溶液，再向该溶液中加入5~8 g高锰酸钾及3~4 g钨酸钠，60~70℃水浴中搅拌10～50分钟，再加入2~3 g甘氨酸，将溶液转移至水热反应器中，180~260℃下，反应5~10 h，过滤得到固体，用蒸馏水洗涤3~5遍，80℃烘干，即得到一种钨酸锰复合二氧化锰催化剂。
本发明的优点是：1. 二氯化锰在水热条件下同时和钨酸钠和高锰酸钾反应，形成充分复合的钨酸锰和二氧化锰复合物。2. 二氧化锰和钨酸锰复合可以促进锰氧化物分散，提高污染物降解速度。
具体实施方式
以下进一步提供本发明的3个实施例：
实施例1
将10 g二氯化锰加入到100 mL水中配制成溶液，再向该溶液中加入8 g高锰酸钾及4 g钨酸钠，70℃水浴中搅拌50分钟，再加入3 g甘氨酸，将溶液转移至水热反应器中， 260℃下，反应10 h，过滤得到固体，用蒸馏水洗涤5遍，80℃烘干，即得到一种钨酸锰复合二氧化锰催化剂。
0.5 g钨酸锰复合二氧化锰催化剂加入到200 mL 浓度为25 mg/L 的亚甲基蓝废水中，在120 W的LED灯照射下，反应100 min，脱色率为96.1%，催化剂分离重复利用5次后，同样条件下，反应100 min，脱色率为94.3%。
实施例2
将5 g二氯化锰加入到50 mL水中配制成溶液，再向该溶液中加入5 g高锰酸钾及3 g钨酸钠，60℃水浴中搅拌10分钟，再加入2 g甘氨酸，将溶液转移至水热反应器中，180℃下，反应5 h，过滤得到固体，用蒸馏水洗涤3遍，80℃烘干，即得到一种钨酸锰复合二氧化锰催化剂。
0.5 g钨酸锰复合二氧化锰催化剂加入到300 mL 浓度为25 mg/L 的酸性大红废水中，在120 W的LED灯照射下，反应100 min，脱色率为96.3%，催化剂分离重复利用5次后，同样条件下，反应100 min，脱色率为92.1%。
实施例3
将8 g二氯化锰加入到80 mL水中配制成溶液，再向该溶液中加入8 g高锰酸钾及4 g钨酸钠， 70℃水浴中搅拌40分钟，再加入3 g甘氨酸，将溶液转移至水热反应器中，200℃下，反应10 h，过滤得到固体，用蒸馏水洗涤4遍，80℃烘干，即得到一种钨酸锰复合二氧化锰催化剂。
0.5 g钨酸锰复合二氧化锰催化剂加入到300 mL 浓度为25 mg/L 的罗丹明B废水中，在120 W的LED灯照射下，反应100 min，脱色率为95.1%，催化剂分离重复利用5次后，同样条件下，反应100 min，脱色率为90.2%。
Claims (1)
1.一种钨酸锰复合二氧化锰催化剂的制备方法，其特征是依次包括如下步骤：
将5~10 g二氯化锰加入到50~100 mL水中配制成溶液，再向该溶液中加入5~8 g高锰酸钾及3~4 g钨酸钠，60~70℃水浴中搅拌10～50分钟，再加入2~3 g甘氨酸，将溶液转移至水热反应器中，180~260℃下，反应5~10 h，过滤得到固体，用蒸馏水洗涤3~5遍，80℃烘干，即得到一种钨酸锰复合二氧化锰催化剂。
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| CN112495372A (zh) * | 2020-11-16 | 2021-03-16 | 华南理工大学 | W-Mn双金属氧化物复合型脱硝催化剂及其制备方法和应用 |
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