TWI467024B - And a method of reducing the metal oxide particles into metal elements - Google Patents
And a method of reducing the metal oxide particles into metal elements Download PDFInfo
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本發明是有關於一種將金屬氧化物粒子還原成金屬元素的方法，特別是指一種使用溶劑及氣態有機酸將金屬氧化物粒子還原成金屬元素的方法。The present invention relates to a method for reducing metal oxide particles to a metal element, and more particularly to a method for reducing metal oxide particles to a metal element using a solvent and a gaseous organic acid.
金屬氧化物粒子還原成金屬元素的方法，包含以下步驟：將複數個金屬氧化物粒子與一還原劑接觸，並施予一加熱處理，以使該等金屬氧化物粒子進行還原反應。舉例來說，將複數個氧化銅粒子或氧化亞銅粒子與氫氣接觸，並加熱至400℃以上，可使得該等氧化銅粒子或氧化亞銅粒子還原成銅元素；又例如，將複數個氧化銅粒子或氧化亞銅粒子與碳接觸，並加熱至500℃以上，可使得該等氧化銅粒子或氧化亞銅粒子還原成銅元素。The method for reducing a metal oxide particle into a metal element comprises the steps of: contacting a plurality of metal oxide particles with a reducing agent, and applying a heat treatment to cause the metal oxide particles to undergo a reduction reaction. For example, contacting a plurality of copper oxide particles or cuprous oxide particles with hydrogen gas and heating to above 400 ° C may cause the copper oxide particles or cuprous oxide particles to be reduced to copper; for example, oxidizing a plurality of oxides The copper particles or cuprous oxide particles are in contact with carbon and heated to 500 ° C or higher to reduce the copper oxide particles or cuprous oxide particles to copper.
上述方法雖可使金屬氧化物粒子還原成金屬元素，然，於該方法中，該等金屬氧化物粒子在還原過程中，因為比表面積(表面積/體積比)大，因而傾向以團聚方式來降低表面積，因此，於高溫(大於400℃以上)時，原子擴散速率快，易發生團聚，使得所形成的金屬元素粒子的粒徑無法與金屬氧化物粒子的粒徑相當，且粒徑粗大，同時粒徑大小不均，並且無法獲得均勻分散的金屬元素粒 子，不利於後續應用，再者，使用具有***性的氫氣，於高溫條件下使用時具有危險性，且上述方法的加熱溫度需至少400℃以上，屬於高耗能的製備方法。Although the above method can reduce the metal oxide particles to a metal element, in the method, since the metal oxide particles have a large specific surface area (surface area/volume ratio) during the reduction, they tend to be reduced by agglomeration. Surface area, therefore, at high temperatures (above 400 ° C or more), the atom diffusion rate is fast, and agglomeration is apt to occur, so that the particle size of the formed metal element particles cannot be equal to the particle size of the metal oxide particles, and the particle size is coarse, and at the same time Uneven particle size and inability to obtain uniformly dispersed metal element particles It is not conducive to subsequent applications. Furthermore, the use of explosive hydrogen gas is dangerous when used under high temperature conditions, and the heating temperature of the above method needs to be at least 400 ° C or more, which is a high energy-consuming preparation method.
有鑑於上述，改良金屬氧化物粒子還原成金屬元素的方法以使所獲得的金屬元素的粒徑與金屬氧化物粒子的粒徑相當，同時，獲得均勻分散的金屬元素粒子，並且提供一低溫操作下即可將金屬氧化物粒子還原成金屬元素的方法，是此技術領域相關技術人員可再突破的課題。In view of the above, a method for reducing the reduction of metal oxide particles into a metal element is such that the particle diameter of the obtained metal element is equivalent to the particle diameter of the metal oxide particles, and at the same time, uniformly dispersed metal element particles are obtained, and a low temperature operation is provided. The method of reducing metal oxide particles to metal elements can be a subject that can be further broken by those skilled in the art.
因此，本發明之目的，即在提供一種將金屬氧化物粒子還原成金屬元素的方法。該方法可使金屬氧化物粒子於還原反應的過程中具有較佳的分散效果，而不會團聚，繼而使所獲得的金屬元素的粒徑與金屬氧化物粒子的粒徑相當，同時，獲得均勻分散的金屬元素粒子，且於300℃溫度以下即可將金屬氧化物粒子還原成金屬元素。Accordingly, it is an object of the present invention to provide a method of reducing metal oxide particles to metal elements. The method can make the metal oxide particles have a better dispersing effect in the process of the reduction reaction without agglomeration, and then the particle size of the obtained metal element is equivalent to the particle diameter of the metal oxide particles, and at the same time, uniformity is obtained. The metal element particles are dispersed and reduced to a metal element at a temperature of 300 ° C or lower.
於是本發明將金屬氧化物粒子還原成金屬元素的方法，包含以下步驟：將複數個金屬氧化物粒子分散於溶劑中，形成一非均相混合液；將該非均相混合液置於一存在氣態有機酸的環境中，並對該非均相混合液施予一加熱處理，以使該等金屬氧化物粒子進行還原反應，其中，該溶劑的沸點溫度範圍為該氣態有機酸的沸點溫度至300℃間。Therefore, the method for reducing metal oxide particles into a metal element according to the present invention comprises the steps of: dispersing a plurality of metal oxide particles in a solvent to form a heterogeneous mixed liquid; and placing the heterogeneous mixed liquid in a gaseous state. In an environment of an organic acid, a heat treatment is applied to the heterogeneous mixed solution to cause the metal oxide particles to undergo a reduction reaction, wherein the solvent has a boiling temperature ranging from a boiling temperature of the gaseous organic acid to 300 ° C. between.
本發明之功效在於：該方法透過溶劑的使用，可使該等金屬氧化物粒子在還原反應的過程中具有較佳的分散效果，而不會團聚，繼而使所獲得的金屬元素的粒徑與金屬氧化物粒子的粒徑相當，同時，獲得均勻分散的金屬元素粒子。The effect of the invention is that the method can make the metal oxide particles have a better dispersing effect during the reduction reaction without using a solvent, and does not agglomerate, and then the particle size of the obtained metal element is The particle diameter of the metal oxide particles is equivalent, and at the same time, uniformly dispersed metal element particles are obtained.
以下將就本發明內容進行詳細說明：較佳地，本發明將金屬氧化物粒子還原成金屬元素的方法中，該溶劑是擇自於乙二醇、丙二醇，或此等一組合。Hereinafter, the present invention will be described in detail. Preferably, in the method of the present invention for reducing metal oxide particles into a metal element, the solvent is selected from ethylene glycol, propylene glycol, or a combination thereof.
較佳地，本發明將金屬氧化物粒子還原成金屬元素的方法中，該金屬氧化物粒子是擇自於氧化銅、氧化亞銅、氧化鋅、氧化銀、氧化鎳、氧化鋁，或此等一組合。Preferably, in the method of the present invention for reducing metal oxide particles into a metal element, the metal oxide particles are selected from copper oxide, cuprous oxide, zinc oxide, silver oxide, nickel oxide, aluminum oxide, or the like. A combination.
較佳地，本發明將金屬氧化物粒子還原成金屬元素的方法中，該氣態有機酸是擇自於甲酸、乙酸，或此等一組合。Preferably, in the method of the invention for reducing metal oxide particles to a metal element, the gaseous organic acid is selected from formic acid, acetic acid, or a combination thereof.
本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中：圖1是一照片，用來說明本發明將氧化亞銅粒子及氧化銅粒子還原成銅金屬元素的方法中，氧化亞銅粒子及氧化銅粒子的粒徑大小與分散程度；圖2是一照片，用來說明本發明將氧化亞銅粒子及氧化銅粒子還原成銅金屬元素的方法中，銅金屬元素的粒徑大 小與分散程度；圖3是一X-ray繞射圖，用來說明本發明使用氧化亞銅粒子及氧化銅粒子的晶相；及圖4是一X-ray繞射圖，用來說明本發明將氧化亞銅粒子及氧化銅粒子還原成銅金屬元素粒子的方法確實可獲得銅金屬元素。Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a photograph illustrating the reduction of cuprous oxide particles and copper oxide particles into copper metal elements according to the present invention. In the method, the particle size and the degree of dispersion of the cuprous oxide particles and the copper oxide particles; FIG. 2 is a photograph for explaining the method for reducing the cuprous oxide particles and the copper oxide particles into copper metal elements according to the present invention, copper metal Large particle size Figure 3 is an X-ray diffraction pattern for illustrating the crystal phase of the cuprous oxide particles and copper oxide particles of the present invention; and Figure 4 is an X-ray diffraction pattern for illustrating the present invention. In the invention, a method of reducing cuprous oxide particles and copper oxide particles into copper metal element particles can surely obtain a copper metal element.
本發明將金屬氧化物粒子還原成金屬元素的方法，包含以下步驟：將複數個金屬氧化物粒子分散於溶劑中，形成一非均相混合液；將該非均相混合液置於一存在氣態有機酸的環境中，並對該非均相混合液施予一加熱處理，以使該等金屬氧化物粒子進行還原反應，其中，該溶劑的沸點溫度範圍為該氣態有機酸的沸點溫度至300℃間。The method for reducing metal oxide particles into a metal element according to the present invention comprises the steps of: dispersing a plurality of metal oxide particles in a solvent to form a heterogeneous mixed liquid; and placing the heterogeneous mixed liquid in a gaseous organic state In an acid environment, a heat treatment is applied to the heterogeneous mixed solution to cause the metal oxide particles to undergo a reduction reaction, wherein the solvent has a boiling temperature ranging from a boiling temperature of the gaseous organic acid to 300 ° C. .
<<金屬氧化物粒子>><<Metal oxide particles>>
該金屬氧化物粒子可單獨或混合使用，且該金屬氧化物粒子例如但不限於氧化銅(CuO)、氧化亞銅(Cu2 O)、氧化鋅(ZnO)、氧化銀(Ag2 O)、氧化鎳(NiO)，或氧化鋁(Al2 O3 )等。The metal oxide particles may be used singly or in combination, and the metal oxide particles are, for example but not limited to, copper oxide (CuO), cuprous oxide (Cu 2 O), zinc oxide (ZnO), silver oxide (Ag 2 O), Nickel oxide (NiO), or aluminum oxide (Al 2 O 3 ) or the like.
該金屬氧化物粒子的平均粒徑範圍為1μm至1,000μm。The metal oxide particles have an average particle diameter ranging from 1 μm to 1,000 μm.
<<溶劑>><<Solvent>>
該溶劑為多元醇。該多元醇可單獨或混合使 用，且該多元醇例如但不限於乙二醇或丙二醇等。The solvent is a polyol. The polyol can be used alone or in combination And the polyol is, for example but not limited to, ethylene glycol or propylene glycol or the like.
<<氣態有機酸>><<Gaseous organic acid>>
該氣態有機酸可單獨或混合使用，且該氣態有機酸例如但不限於甲酸或乙酸等。The gaseous organic acid may be used singly or in combination, and the gaseous organic acid is, for example, but not limited to, formic acid or acetic acid.
該加熱處理的操作溫度為使該等金屬氧化物粒子與該氣態有機酸可進行還原反應的溫度即可。The operation temperature of the heat treatment may be a temperature at which the metal oxide particles and the gaseous organic acid can undergo a reduction reaction.
本發明將就以下實施例來作進一步說明，但應 瞭解的是，該等實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The invention will be further illustrated by the following examples, but It is understood that the examples are for illustrative purposes only and are not to be construed as limiting.
<<實施例>><<Example>>
<<實施例1>><<Example 1>>
提供一包含氧化亞銅粒子及氧化銅粒子的混合物，且該混合物的平均粒徑為0.5μm。將1克的混合物置於室溫(25℃)下分散於70毫升的乙二醇中，形成一非均相混合液。將該非均相混合液置於一存在氣態甲酸的環境中，並對該非均相混合液施予250℃的加熱溫度，以使該等氧化亞銅粒子進行還原反應，且反應0.5小時。待反應後停止通入氣態甲酸，並導入氬氣及氮氣，同時，進行降溫。A mixture comprising cuprous oxide particles and copper oxide particles is provided, and the mixture has an average particle diameter of 0.5 μm. One gram of the mixture was dispersed in 70 ml of ethylene glycol at room temperature (25 ° C) to form a heterogeneous mixture. The heterogeneous mixed solution was placed in an environment in which gaseous formic acid was present, and the heterogeneous mixed liquid was subjected to a heating temperature of 250 ° C to carry out a reduction reaction of the cuprous oxide particles, and the reaction was carried out for 0.5 hour. After the reaction, the gaseous formic acid was stopped, and argon gas and nitrogen gas were introduced, and at the same time, the temperature was lowered.
<<評價項目>><<Evaluation project>>
分散性量測：使用掃描式電子顯微鏡(廠牌：JEOL；型號：6700F)觀察實施例1中所使用的混合物，以及實施例1所獲得的銅金屬元素的分散情況，如圖1及圖2。Dispersibility measurement: The mixture used in Example 1 and the dispersion of the copper metal element obtained in Example 1 were observed using a scanning electron microscope (label: JEOL; model: 6700F), as shown in Fig. 1 and Fig. 2 .
相鑑定分析：使用X-ray繞射儀(廠牌：Bruker；型號：D8 SSS)分析實施例1中所使用的混合物，以及經還原處理後所獲得的產物，分別如圖3及圖4所示。Phase identification analysis: The mixture used in Example 1 and the product obtained after reduction treatment were analyzed using an X-ray diffractometer (label: Bruker; model: D8 SSS), as shown in Figures 3 and 4, respectively. Show.
由圖2可知，使用本案的方法確實可使所獲得的銅金屬元素的粒徑與混合物中的氧化銅粒子或氧化亞銅粒子的粒徑相當，表示於還原反應過程中氧化銅粒子或氧化亞銅粒子確實無團聚現象發生，同時，也獲得均勻分散的銅金屬元素粒子。It can be seen from Fig. 2 that the method of the present invention can make the particle size of the obtained copper metal element equivalent to the particle size of the copper oxide particles or the cuprous oxide particles in the mixture, which is represented by the copper oxide particles or the oxidized sub-process during the reduction reaction. The copper particles do not agglomerate, and at the same time, uniformly dispersed copper metal element particles are obtained.
根據JCPDS-ICDD資料編號Cu：04-0836；Cu2 O：05-0667；CuO：05-0661，並搭配圖3及圖4可知，使用本案的方法確實可使氧化銅粒子及氧化亞銅粒子還原成銅金屬元素。According to JCPDS-ICDD data No. Cu: 04-0836; Cu 2 O: 05-0667; CuO: 05-0661, and with FIG. 3 and FIG. 4, it is known that the copper oxide particles and cuprous oxide particles can be obtained by the method of the present invention. Reduced to copper metal elements.
綜上所述，本案的方法透過溶劑的使用，可使該等金屬氧化物粒子在還原反應的過程中具有較佳的分散效果，而不會團聚，繼而使所獲得的金屬元素粒徑與金屬氧化物粒子的粒徑相當，同時，獲得均勻分散的金屬元素粒子，故確實能達成本發明之目的。In summary, the method of the present invention allows the metal oxide particles to have a better dispersion effect during the reduction reaction through the use of a solvent without agglomeration, and then the obtained metal element particle size and metal. The particle diameter of the oxide particles is equivalent, and at the same time, the uniformly dispersed metal element particles are obtained, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.
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