TWI573765B - Catalyst for removing hydrogen peroxide in water and its preparation method - Google Patents

Catalyst for removing hydrogen peroxide in water and its preparation method Download PDF

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TWI573765B
TWI573765B TW103132019A TW103132019A TWI573765B TW I573765 B TWI573765 B TW I573765B TW 103132019 A TW103132019 A TW 103132019A TW 103132019 A TW103132019 A TW 103132019A TW I573765 B TWI573765 B TW I573765B
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catalyst
oxide
porous carrier
hydrogen peroxide
proportion
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TW103132019A
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TW201612113A (en
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Yu Chia Chiu
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Zetech Engineering And Services Ltd
Gao Hui-Lin
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去除水中雙氧水的觸媒及其製備方法 Catalyst for removing hydrogen peroxide in water and preparation method thereof

本發明係關於一種觸媒及其製備方法,尤為一種去除水中雙氧水的觸媒及其製備方法。 The invention relates to a catalyst and a preparation method thereof, in particular to a catalyst for removing hydrogen peroxide in water and a preparation method thereof.

近年來,隨環保意識提高及法規趨於嚴謹下,對於工業廢水之回收也日亦受到重視,其中為減少雙氧水對水質的汙染以及對設備腐蝕,如何去除水中雙氧水的方法為其主要努力重點之一,目前對於去除廢水中雙氧水的方式而言,多數普遍採用活性碳進行處理,但活性碳塔床缺點在於需具備龐大的設備體積,且雙氧水之氧化性容易使塔床中的活性碳粉末化,活性碳粉末化可能導致設備壓降的增大,更進一步影響操作參數無法有效掌握,造成整體處理效率降低,故尋求一有效之媒介,替代活性碳塔床去除水中雙氧水,為各方所努力之方向。 In recent years, with the improvement of environmental awareness and the rigorous regulations, the recycling of industrial wastewater has also received attention. In order to reduce the pollution of water quality and corrosion of equipment by hydrogen peroxide, how to remove hydrogen peroxide from water is the main focus of its efforts. First, at present, most of the methods for removing hydrogen peroxide in wastewater are treated with activated carbon. However, the disadvantage of the activated carbon column bed is that it requires a large equipment volume, and the oxidation of hydrogen peroxide is easy to make the activated carbon powder in the tower bed. The activation of activated carbon powder may lead to an increase in equipment pressure drop, further affecting the inability to effectively control the operating parameters, resulting in a reduction in overall processing efficiency. Therefore, an effective medium is sought to replace the activated carbon tower bed to remove hydrogen peroxide in water. The direction of the effort.

由此可見,上述現有去除廢水中雙氧水技術仍有諸多缺失,實非一良善之設計,而亟待加以改良。 It can be seen that the above-mentioned existing technology for removing hydrogen peroxide from wastewater has many defects, which is not a good design and needs to be improved.

本發明提供一種去除水中雙氧水的觸媒,其結構係為一多孔性載體做為其核心,在多孔性載體表面外層塗佈一過渡金屬氧化層。 The invention provides a catalyst for removing hydrogen peroxide in water, the structure of which is a porous carrier as its core, and a transition metal oxide layer is coated on the outer surface of the porous carrier.

其中多孔性載體係為氧化矽、氧化鋁、氧化錳、沸石、活性碳及矽藻土之一或二者以上所組成,此多孔性載體之比重介於0.4~1.5g/cm3之間,且多孔性載體之比表面積大於200m2/g。其中該過渡金屬氧化層係塗佈於多孔性載體之表面,其重量佔觸媒總重量的3~30%,而過渡金屬氧化層中錳氧化物比例佔50~80%、鈦氧化物比例佔0~20%、鐵氧化物比例佔0~20%及銅氧化物比例佔0~20%。 The porous carrier is composed of one or more of cerium oxide, aluminum oxide, manganese oxide, zeolite, activated carbon and diatomaceous earth, and the specific gravity of the porous carrier is between 0.4 and 1.5 g/cm 3 . Further, the porous carrier has a specific surface area of more than 200 m 2 /g. Wherein the transition metal oxide layer is coated on the surface of the porous carrier, the weight of which is 3~30% of the total weight of the catalyst, and the proportion of manganese oxide in the transition metal oxide layer accounts for 50-80%, and the proportion of titanium oxide accounts for 0~20%, the proportion of iron oxides is 0~20%, and the proportion of copper oxides is 0~20%.

本發明提供一種去除水中雙氧水的觸媒之製備方法,步驟如下:將含錳、鈦、鐵、銅之化合物及水均勻混和形成一金屬離子混合溶液;將一多孔性載體浸於該金屬離子混合液中,靜置至少1小時(22~24小時為較佳),形成一觸媒前驅物;將觸媒前驅物風乾至少1小時(20~24小時為較佳),以100~600℃(250~300℃為較佳)烘乾至少1小時(6~8小時為較佳),完成過渡金屬氧化層的金屬離子氧化及塗佈,形成一觸媒。 The invention provides a preparation method of a catalyst for removing hydrogen peroxide in water, the steps are as follows: uniformly mixing a compound containing manganese, titanium, iron and copper and water to form a metal ion mixed solution; immersing a porous carrier in the metal ion In the mixed solution, let stand for at least 1 hour (22~24 hours is preferred) to form a catalyst precursor; air dry the catalyst precursor for at least 1 hour (20~24 hours is preferred), 100~600 °C (250~300 °C is preferred) Drying for at least 1 hour (6~8 hours is preferred), complete the metal ion oxidation and coating of the transition metal oxide layer to form a catalyst.

其中更包含一多孔性載體之製備步驟,步驟如下:將氧化矽、氧化鋁、氧化錳、矽藻土及沸石其中之一或二者以上、黏著劑及造粒劑混合均勻,形成一多孔性載體前驅物;以及將該載體前驅物以600~1200℃(800~900℃為較佳)燒結一至少1小時(5~6小時為較佳),形成多孔性載體。 The method further comprises the steps of: preparing a porous carrier, the steps are as follows: mixing one or more of cerium oxide, aluminum oxide, manganese oxide, diatomaceous earth and zeolite, an adhesive and a granulating agent to form a plurality of The porous carrier precursor; and the carrier precursor is sintered at 600 to 1200 ° C (800 to 900 ° C is preferred) for at least one hour (5 to 6 hours is preferred) to form a porous carrier.

上列詳細說明係針對本發明之一可行實施例之具體說明,惟該實施例並非用以限制本發明之專利範圍,凡未脫離本發明技藝精神所為之等效實施或變更,均應包含於本案之專利範圍中。 The detailed description of the preferred embodiments of the present invention is intended to be limited to the scope of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.

綜上所述,本案不但在空間型態上確屬創新,並能較習用物品增進上述多項功效,應已充分符合新穎性及進步性之法定發明專利要件,爰依法提出申請,懇請 貴局核准本件發明專利申請案,以勵發明,至感德便。 In summary, this case is not only innovative in terms of space type, but also can enhance the above-mentioned multiple functions compared with the customary items. It should fully meet the statutory invention patent requirements of novelty and progressiveness, and apply for it according to law. This invention patent application, in order to invent invention, to the sense of virtue.

10‧‧‧觸媒 10‧‧‧ catalyst

11‧‧‧多孔性載體 11‧‧‧Porous carrier

12‧‧‧過渡金屬氧化層 12‧‧‧Transition metal oxide layer

S201~S203‧‧‧步驟流程 S201~S203‧‧‧Step process

S301~S303‧‧‧步驟流程 S301~S303‧‧‧Step procedure

S401~S402‧‧‧步驟流程 S401~S402‧‧‧Step procedure

S501~S502‧‧‧步驟流程 S501~S502‧‧‧Step procedure

第1圖為本發明之去除水中雙氧水的觸媒之結構示意圖 Figure 1 is a schematic view showing the structure of a catalyst for removing hydrogen peroxide in water according to the present invention.

第2圖為本發明之去除水中雙氧水的觸媒之製備方法流程圖。 Fig. 2 is a flow chart showing the preparation method of the catalyst for removing hydrogen peroxide in water according to the present invention.

第3圖為本發明之去除水中雙氧水的觸媒之另一製備方法流程圖 Figure 3 is a flow chart showing another preparation method of the catalyst for removing hydrogen peroxide in water according to the present invention.

第4圖為本發明之多孔性載體之製備方法流程圖。 Figure 4 is a flow chart showing the preparation method of the porous carrier of the present invention.

第5圖為本發明之多孔性載體之另一製備方法流程圖。 Figure 5 is a flow chart showing another method of preparing the porous carrier of the present invention.

第6圖為本發明之去除水中雙氧水的觸媒之效率關係圖。 Figure 6 is a graph showing the efficiency of the catalyst for removing hydrogen peroxide in water according to the present invention.

為利 貴審查委員了解本發明之技術特徵、內容與優點及其所能達到之功效,茲將本發明配合附圖,並以實施例之表達形式詳細說明如下,而其中所使用之圖式,其主旨僅為示意及輔助說明書之用,未必為本發明實施後之真實比例與精準配置,故不應就所附之圖式的比例與配置關係解讀、侷限本發明於實際實施上的權利範圍,合先敘明。 The technical features, contents, and advantages of the present invention, as well as the advantages thereof, can be understood by the reviewing committee, and the present invention will be described in detail with reference to the accompanying drawings. The subject matter is only for the purpose of illustration and description. It is not intended to be a true proportion and precise configuration after the implementation of the present invention. Therefore, the scope and configuration relationship of the attached drawings should not be interpreted or limited. First described.

請參閱第1圖,如圖所示,為本發明之去除水中雙氧水的觸媒之結構示意圖,其中觸媒10,具有多孔性載體11做為一核心,該多孔性載體11表面外層塗佈一過渡金屬氧化層12,而此過渡金屬氧化層12之過 渡金屬氧化物係為錳氧化物、鈦氧化物、鐵氧化物及銅氧化物所組成。 Please refer to FIG. 1 , which is a schematic structural view of a catalyst for removing hydrogen peroxide in water according to the present invention, wherein the catalyst 10 has a porous carrier 11 as a core, and the outer surface of the porous carrier 11 is coated with a coating. Transition metal oxide layer 12, and transition metal oxide layer 12 The metal oxide is composed of manganese oxide, titanium oxide, iron oxide and copper oxide.

其中多孔性載體11係為氧化矽、氧化鋁、氧化錳、沸石、活性碳及矽藻土之一或二者以上之組合,其多孔性載體11之比重介於0.4~1.5g/cm3之間,且該多孔性載體11之比表面積大於200m2/g。其中該過渡金屬氧化層12之重量比例佔觸媒總重量的3~30%,而該過渡金屬氧化層中錳氧化物比例佔50~80%、鈦氧化物比例佔0~20%、鐵氧化物比例佔0~20%及銅氧化物比例佔0~20%。 The porous carrier 11 is a combination of one or more of cerium oxide, aluminum oxide, manganese oxide, zeolite, activated carbon and diatomaceous earth, and the specific gravity of the porous carrier 11 is between 0.4 and 1.5 g/cm 3 . The porous carrier 11 has a specific surface area of more than 200 m 2 /g. Wherein the weight ratio of the transition metal oxide layer 12 accounts for 3 to 30% of the total weight of the catalyst, and the proportion of manganese oxide in the transition metal oxide layer accounts for 50-80%, the proportion of titanium oxide accounts for 0-20%, and iron oxide The proportion of materials accounts for 0~20% and the proportion of copper oxide accounts for 0~20%.

請參閱第2圖,為本發明之去除水中雙氧水的觸媒之製備方法流程圖,步驟如下:S201:將含錳、鈦、鐵、銅之化合物及水均勻混和形成一金屬離子混合溶液;S202:將多孔性載體浸於該金屬離子混合液中,靜置至少1小時,形成一觸媒前驅物;S203:該觸媒前驅物風乾至少1小時,以100~600℃烘乾至少1小時,完成過渡金屬氧化層的金屬離子氧化及塗佈,形成一觸媒。 2 is a flow chart of a method for preparing a catalyst for removing hydrogen peroxide in water according to the present invention. The steps are as follows: S201: uniformly mixing a compound containing manganese, titanium, iron, copper and water to form a metal ion mixed solution; S202 : immersing the porous carrier in the metal ion mixture and allowing to stand for at least 1 hour to form a catalyst precursor; S203: drying the catalyst precursor for at least 1 hour, drying at 100 to 600 ° C for at least 1 hour, The metal ion of the transition metal oxide layer is oxidized and coated to form a catalyst.

請參閱第3圖,為本發明之去除水中雙氧水的觸媒之另一製備方法流程圖,步驟如下:S301:將含錳、鈦、鐵、銅之化合物及水均勻混和形成一金屬離子混合溶液;S302:將多孔性載體浸於該金屬離子混合液中,靜置22~24小時,形成一觸媒前驅物;S303:該觸媒前驅物風乾20~24小時,以250~300℃烘乾6~8小時,完成 過渡金屬氧化層的金屬離子氧化及塗佈,形成一觸媒。 Please refer to FIG. 3 , which is a flow chart of another preparation method of the catalyst for removing hydrogen peroxide in water according to the present invention. The steps are as follows: S301: uniformly mixing a compound containing manganese, titanium, iron, copper and water to form a metal ion mixed solution. S302: immersing the porous carrier in the metal ion mixture, and standing for 22 to 24 hours to form a catalyst precursor; S303: the catalyst precursor is air-dried for 20 to 24 hours, and dried at 250 to 300 ° C; 6~8 hours, completed The metal ions of the transition metal oxide layer are oxidized and coated to form a catalyst.

請參閱第4圖,為本發明之多孔性載體之製備方法流程圖,步驟如下:S401:將氧化矽、氧化鋁、氧化錳、沸石及矽藻土之一或二者以上、黏著劑及造粒劑混合均勻,形成一多孔性載體前驅物;以及S402:將多孔性載體前驅物以600~1200℃燒結一至少1小時,形成多孔性載體。 Please refer to FIG. 4 , which is a flow chart of a method for preparing a porous carrier according to the present invention. The steps are as follows: S401: one or more of cerium oxide, aluminum oxide, manganese oxide, zeolite and diatomaceous earth, adhesive and preparation The granules are uniformly mixed to form a porous carrier precursor; and S402: the porous carrier precursor is sintered at 600 to 1200 ° C for at least one hour to form a porous carrier.

請參閱第5圖,為本發明之多孔性載體之另一製備方法流程圖,步驟如下:S501:將氧化矽、氧化鋁、氧化錳、沸石及矽藻土之一或二者以上、黏著劑及造粒劑混合均勻,形成一多孔性載體前驅物;以及S502:將多孔性載體前驅物以800~900℃燒結5~6小時,形成多孔性載體。 Please refer to FIG. 5 , which is a flow chart of another preparation method of the porous carrier of the present invention, and the steps are as follows: S501: one or more of cerium oxide, aluminum oxide, manganese oxide, zeolite and diatomaceous earth, and an adhesive. And the granulating agent is uniformly mixed to form a porous carrier precursor; and S502: the porous carrier precursor is sintered at 800 to 900 ° C for 5 to 6 hours to form a porous carrier.

請參閱第6圖,為本發明之去除水中雙氧水的觸媒之效率關係圖,本發明之觸媒於雙氧水濃度500mg/L的水中,停留時間1.5~4分鐘之效率關係圖,當觸媒於停留時間1.5分鐘以上時,相較於同體積之活性碳,本發明之觸媒所去除水中雙氧水之效率約80~98%,為同體積之活性碳去除水中雙氧水之效率的兩倍以上,且去除效率隨觸媒停留時間增加而提高。由此可知,當去除水中雙氧水之效率相同情況下,本發明之觸媒所需體積僅為活性碳的1/2甚至更少,相較之下本發明之觸媒具有更佳的雙氧水去除效率,此不僅解決傳統活性碳粉末化之問題,進一步可減少廢水停留處理的時間,縮減整體時程,並節省龐大的活性碳塔之空間,實為一省時省能之發明。 Please refer to FIG. 6 , which is a graph showing the efficiency relationship of the catalyst for removing hydrogen peroxide in water according to the present invention. The efficiency of the catalyst of the present invention in a water having a hydrogen peroxide concentration of 500 mg/L and a residence time of 1.5 to 4 minutes is as shown in the catalyst. When the residence time is 1.5 minutes or more, the catalyst of the present invention has an efficiency of removing 80% to 98% of hydrogen peroxide in water compared with the same volume of activated carbon, which is more than twice the efficiency of the same volume of activated carbon to remove hydrogen peroxide in water, and The removal efficiency increases as the catalyst residence time increases. It can be seen that when the efficiency of removing hydrogen peroxide in water is the same, the required volume of the catalyst of the present invention is only 1/2 or less of that of activated carbon, and the catalyst of the present invention has better hydrogen peroxide removal efficiency. This not only solves the problem of traditional activated carbon powdering, but also reduces the time for wastewater treatment, reduces the overall time course, and saves space for a large activated carbon tower, which is a time-saving and energy-saving invention.

上列詳細說明乃針對本發明之一可行實施例進行具體說明,惟該實施例並非用以限制本發明之專利範圍,凡未脫離本發明技藝精神所為之等效實施或變更,均應包含於本案之專利範圍中。 The detailed description of the present invention is intended to be illustrative of a preferred embodiment of the invention, and is not intended to limit the scope of the invention. The patent scope of this case.

綜上所述,本案不僅於技術思想上確屬創新,並具備習用之傳統方法所不及之上述多項功效,已充分符合新穎性及進步性之法定發明專利要件,爰依法提出申請,懇請 貴局核准本件發明專利申請案,以勵發明,至感德便。 To sum up, this case is not only innovative in terms of technical thinking, but also has many of the above-mentioned functions that are not in the traditional methods of the past. It has fully complied with the statutory invention patent requirements of novelty and progressiveness, and applied for it according to law. Approved this invention patent application, in order to invent invention, to the sense of virtue.

S201~S203‧‧‧步驟流程 S201~S203‧‧‧Step process

Claims (8)

一種去除水中雙氧水的觸媒,係為:一多孔性載體;一過渡金屬氧化層,其中該過渡金屬氧化層係塗佈於該載體之表面;其中該過渡金屬氧化層之重量比例佔觸媒總重量的3~30%;以及其中該過渡金屬氧化層中錳氧化物比例佔50~80%、鈦氧化物比例佔0~20%、鐵氧化物比例佔0~20%及銅氧化物比例佔0~20%。 A catalyst for removing hydrogen peroxide in water is: a porous carrier; a transition metal oxide layer, wherein the transition metal oxide layer is coated on the surface of the carrier; wherein the weight ratio of the transition metal oxide layer accounts for the catalyst 3~30% of the total weight; and the proportion of manganese oxide in the transition metal oxide layer is 50-80%, the proportion of titanium oxide is 0-20%, the proportion of iron oxide is 0-20%, and the proportion of copper oxide Occupy 0~20%. 如申請專利範圍第1項所述之去除水中雙氧水的觸媒,其中該多孔性載體係為氧化矽、氧化鋁、氧化錳、沸石、活性碳及矽藻土之一或二者以上之組合。 The catalyst for removing hydrogen peroxide in water according to claim 1, wherein the porous carrier is one or a combination of two or more of cerium oxide, aluminum oxide, manganese oxide, zeolite, activated carbon and diatomaceous earth. 如申請專利範圍第2項所述之去除水中雙氧水的觸媒,其中該多孔性載體之比重介於0.4~1.5g/cm3之間,該多孔性載體之比表面積大於200m2/g。 The catalyst for removing hydrogen peroxide in water according to claim 2, wherein the porous carrier has a specific gravity of between 0.4 and 1.5 g/cm 3 and the porous carrier has a specific surface area of more than 200 m 2 /g. 一種去除水中雙氧水的觸媒之製備方法,步驟如下:將含錳、鈦、鐵或銅之化合物及水均勻混和形成一金屬離子混合溶液;將一多孔性載體浸於該金屬離子混合液中,靜置一第一時間,形成一觸媒前驅物;該觸媒前驅物風乾一第二時間,以一第一溫度烘乾一第三時間,完成一過渡金屬氧化層塗佈,形成一觸媒。 A method for preparing a catalyst for removing hydrogen peroxide in water is as follows: uniformly mixing a compound containing manganese, titanium, iron or copper and water to form a metal ion mixed solution; immersing a porous carrier in the metal ion mixed solution , standing for a first time, forming a catalyst precursor; the catalyst precursor is dried for a second time, and dried at a first temperature for a third time to complete a transition metal oxide coating to form a touch Media. 如申請專利範圍第4項所述之去除水中雙氧水的觸媒之製備方法,其中更包含一多孔性載體製備方法,步驟如下:將氧化矽、氧化鋁、氧化錳、沸石及矽藻土之一或二者以上、黏著劑及 造粒劑混合均勻,形成一多孔性載體前驅物;將該多孔性載體前驅物以一第二溫度燒結一第四時間,形成該多孔性載體;以及其中該過渡金屬氧化層之重量比例佔觸媒總重量的3~30%,該過渡金屬氧化層中錳氧化物比例佔50~80%、鈦氧化物比例佔0~20%、鐵氧化物比例佔0~20%及銅氧化物比例佔0~20%。 The method for preparing a catalyst for removing hydrogen peroxide in water according to claim 4, further comprising a method for preparing a porous carrier, the steps are as follows: cerium oxide, aluminum oxide, manganese oxide, zeolite and diatomaceous earth One or more, adhesives and The granulating agent is uniformly mixed to form a porous carrier precursor; the porous carrier precursor is sintered at a second temperature for a fourth time to form the porous carrier; and wherein the proportion of the transition metal oxide layer is 3 to 30% of the total weight of the catalyst, the proportion of manganese oxide in the transition metal oxide layer is 50-80%, the proportion of titanium oxide is 0-20%, the proportion of iron oxide is 0-20%, and the proportion of copper oxide Occupy 0~20%. 如申請專利範圍第4項所述之去除水中雙氧水的觸媒之製備方法,其中該第一時間為1小時以上,該第二時間為1小時以上,該第三時間為1小時以上,該第四時間為1小時以上,該第一溫度為100~600℃之間,以及該第二溫度為600~1200℃之間。 The method for preparing a catalyst for removing hydrogen peroxide in water according to claim 4, wherein the first time is 1 hour or longer, the second time is 1 hour or longer, and the third time is 1 hour or longer. The four times are more than one hour, the first temperature is between 100 and 600 ° C, and the second temperature is between 600 and 1200 ° C. 如申請專利範圍第6項所述之去除水中雙氧水的觸媒之製備方法,其中該第一時間進一步為22~24小時,該第二時間進一步為20~24小時,該第三時間進一步為6~8小時,該第四時間進一步為5~6小時,該第一溫度進一步為250~300℃之間,以及該第二溫度進一步為800~900℃之間。 The method for preparing a catalyst for removing hydrogen peroxide in water according to claim 6 , wherein the first time is further 22 to 24 hours, the second time is further 20 to 24 hours, and the third time is further 6 ~8 hours, the fourth time is further 5 to 6 hours, the first temperature is further between 250 and 300 ° C, and the second temperature is further between 800 and 900 ° C. 如申請專利範圍第4項所述之去除水中雙氧水的觸媒之製備方法,其中該多孔性載體係為氧化矽、氧化鋁、氧化錳、沸石、活性碳及矽藻土之一或二者以上之組合。 The method for preparing a catalyst for removing hydrogen peroxide in water according to the fourth aspect of the invention, wherein the porous carrier is one or more of cerium oxide, aluminum oxide, manganese oxide, zeolite, activated carbon and diatomaceous earth. The combination.
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Publication number Priority date Publication date Assignee Title
TWI408107B (en) * 2004-03-31 2013-09-11 Kurita Water Ind Ltd Extra-pure water production equipment and operating method thereof
TWI412404B (en) * 2010-12-08 2013-10-21 Ind Tech Res Inst Catalysts and methods for manufacturing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI408107B (en) * 2004-03-31 2013-09-11 Kurita Water Ind Ltd Extra-pure water production equipment and operating method thereof
TWI412404B (en) * 2010-12-08 2013-10-21 Ind Tech Res Inst Catalysts and methods for manufacturing the same

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