TWI392663B - The application of mo-doped nicob catalyst for hydrogenation for chloronitrobenzene - Google Patents
The application of mo-doped nicob catalyst for hydrogenation for chloronitrobenzene Download PDFInfo
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本發明係一種以鉬為促進劑改質之鎳鈷硼觸媒在含氯硝基苯氫化反應的應用，尤指一種於水溶液中以硼氫化物為還原劑經化學還原法還原鎳鹽、鈷鹽與鉬鹽混合物製造鉬-鎳鈷硼奈米非晶態觸媒的方法，並用於含氯硝基苯之液相氫化反應。 The invention relates to a nickel-cobalt-boron catalyst modified by using molybdenum as a promoter in the hydrogenation reaction of chloronitrobenzene, in particular to reducing nickel salt and cobalt by chemical reduction method using borohydride as a reducing agent in aqueous solution. A method for producing a molybdenum-nickel cobalt boron nano-amorphous catalyst by mixing a salt with a molybdenum salt, and for use in a liquid phase hydrogenation reaction of chloronitrobenzene.
現今的觸媒領域中，奈米技術與非晶態(amorphous)結構是研究中的兩大主題。一般而言，當觸媒粒徑達到奈米級之大小時，其催化性質與巨觀顆粒開始有顯著的差異，即稱之為奈米觸媒。奈米觸媒依其定義來說，主要可分為以下幾種：依顆粒直徑定義-顆粒直徑小於100奈米即稱為奈米觸媒；依孔洞直徑定義-觸媒均為多孔性物質，故有人將孔洞直徑達奈米級，尤其是指小於10奈米的稱為奈米觸媒，例如沸石的孔洞直徑均為奈米級，故亦有人稱其為奈米材料；依孔洞管壁厚度定義，也有人將觸媒孔壁厚度在奈米級的稱為奈米觸媒，亦稱為奈米結構觸媒。非晶(amorphous)合金粒子則由於其本質上許多特殊的特性，因而引起多方的研究，例如：短程無序(short-range order)、長程有序(long-range disorder)和高分散性，它們在粉末冶金學、磁性物質、觸媒的應用潛力極大。當觸媒結合了非晶形及超細合金的特徵，將具有1.高表面不飽和活性位置，2.具有結晶缺陷，3.等方性(isotropic structure)的結構，使其對特定的反應具有高活性、高選擇率及高穩定性的催化性質。 In today's catalyst field, nanotechnology and amorphous structure are two major themes in research. In general, when the particle size of the catalyst reaches the nanometer size, the catalytic properties are significantly different from those of the giant particles, which is called nanocatalyst. According to its definition, nanocatalyst can be divided into the following types: according to the particle diameter definition - the particle diameter is less than 100 nm, which is called nanocatalyst; according to the pore diameter definition - the catalyst is porous material, Therefore, some people have a hole diameter of nanometer, especially a nanocatalyst of less than 10 nanometers. For example, the pore diameter of zeolite is nanometer, so it is also called nanomaterial; Thickness definition, some people have the thickness of the catalyst hole wall in the nanometer called nanocatalyst, also known as nanostructure catalyst. Amorphous alloy particles are subject to various studies due to their many special properties, such as: short-range order, long-range disorder and high dispersion. It has great potential in powder metallurgy, magnetic materials and catalysts. When the catalyst combines the characteristics of amorphous and ultra-fine alloys, it will have 1. high surface unsaturated active sites, 2. crystal defects, 3. isotropic structure, so that it has a specific reaction Highly active, high selectivity and high stability catalytic properties.
鎳觸媒在石化工業上已經廣泛的使用，如未飽和有機物的氫化、加氫 裂解、合成氣甲烷化及水蒸氣重組等等。不過傳統的鎳觸媒容易因為載體孔洞的燒結、不純物堵塞孔洞或反應物殘留在活性基上而造成活性衰退。 Nickel catalysts have been widely used in the petrochemical industry, such as hydrogenation and hydrogenation of unsaturated organics. Cracking, syngas methanation and steam reforming, etc. However, the conventional nickel catalyst is liable to cause deterioration in activity due to sintering of the pores of the carrier, blocking of pores by impurities, or residues remaining on the active group.
本發明揭示以鉬為促進劑改質之鎳鈷硼奈米非晶態觸媒在含氯硝基苯液相氫化反應上的應用。此觸媒係以醋酸鎳、醋酸鈷及鉬酸銨為原料，先將其溶於甲醇與水的混合溶劑中(甲醇與水之體積比介於0.1至1之間)，再以硼氫化物溶液於氮氣流下還原製成奈米微粒，經離心、水洗後，即得具高催化活性之鉬-鎳鈷硼觸媒，其組成可以Moz-NiCoxBy表示，其中x為鈷與鎳之原子比、y為鈷與硼之原子比、z為鉬與鎳之原子比(0.1≦x、y、z≦1)。製備之觸媒粒徑在5奈米至100奈米之間，且為非結晶型態，比表面積介於20~100 m2/g。含氯硝基苯氫化反應係在一淤漿或流動式反應器進行，溶劑為四個碳以下的醇類，氫氣壓力在5至40大氣壓之間，反應溫度為40至150℃之間，此觸媒對於含氯硝基苯的氫化反應，具有高活性與高產物選擇性的特質，含氯苯胺選擇率大於98%。 The invention discloses the application of a nickel-cobalt boron nano-amorphous catalyst modified with molybdenum as a promoter in the liquid phase hydrogenation reaction of chloronitrobenzene. The catalyst is made of nickel acetate, cobalt acetate and ammonium molybdate, and is first dissolved in a mixed solvent of methanol and water (the volume ratio of methanol to water is between 0.1 and 1), followed by borohydride. The solution is reduced to a nanoparticle by a nitrogen stream. After centrifugation and water washing, a molybdenum-nickel-cobalt-boron catalyst having high catalytic activity is obtained, and its composition can be represented by Mo z -NiCo x B y , where x is cobalt and nickel. The atomic ratio, y is the atomic ratio of cobalt to boron, and z is the atomic ratio of molybdenum to nickel (0.1 ≦ x, y, z ≦ 1). The prepared catalyst has a particle size of between 5 nm and 100 nm and is amorphous, and has a specific surface area of 20 to 100 m 2 /g. The chloronitrobenzene hydrogenation reaction is carried out in a slurry or a mobile reactor, the solvent is an alcohol of four carbon or less, the hydrogen pressure is between 5 and 40 atm, and the reaction temperature is between 40 and 150 ° C. The catalyst has high activity and high product selectivity for the hydrogenation reaction of chloronitrobenzene, and the selectivity to chloroaniline is greater than 98%.
奈米金屬微粒因具高表面原子數，表面粗糙程度隨粒徑減小而增加，形成凹凸不平的原子台階，增加了化學反應的接觸面，具有異於塊狀金屬與金屬原子之獨特化學與物理性質。製備金屬奈米微粒的技術有化學還原法、電化學還原法、氣相沉積法、微波輻射法、紫外線光解法、熱分解法等，其中化學還原法因具有容易製備、分散穩定、粒徑較小及分佈較窄的優點，在催化應用上廣為使用。 Due to the high number of surface atoms, the surface roughness of the nano metal particles increases with the decrease of the particle size, forming an uneven atomic step, increasing the contact surface of the chemical reaction, and having a unique chemical relationship different from the bulk metal and the metal atom. Physical properties. The techniques for preparing metal nanoparticles include chemical reduction method, electrochemical reduction method, vapor deposition method, microwave irradiation method, ultraviolet photolysis method, thermal decomposition method, etc., wherein the chemical reduction method has the advantages of easy preparation, stable dispersion, and relatively large particle size. Small and narrowly distributed, it is widely used in catalytic applications.
含氯硝基苯以液態氫化反應生成含氯苯胺的方法，先前技藝均是以貴重金屬為觸媒，其中包括鈀、鉑及釕三種觸媒，用為對氯硝基苯氫化成對氯苯胺，間氯硝基苯氫化成間氯苯胺，Coq[J.Molecular Catalysis，第79卷，第243頁，1993年]以鉑跟釕等貴金屬，探討觸媒晶粒粒徑大小對於對-氯硝基苯的選擇性氫化的影響。Figueras等人之論文[Applied Catalysis，第76卷，第255-266頁，1991年]揭示以釕金屬做為對氯硝基苯之氫化反應觸媒；Liao等人之論文[J.Chem.Soc.,Chem.Comm.，第1155-1156頁，1995年]揭示以鈀-釕雙金屬做為對氯硝基苯之氫化反應觸媒；Vitulli等人之論文[Catalysis Letter，第44卷，第205-210頁，1997年]揭示以鉑/氧化鋁為對氯硝基苯之氫化反應觸媒；Lin等人之論文[J.Molecular Catalysis A：Chemical，第159卷，第115-120頁，2000年]揭示添加界面活性劑polyvinyl alcohol(聚乙烯吡咯酮)在鉑金屬上，做為對氯硝基苯之氫化反應觸媒。美國專利第4,326,078號，揭示以貴重金屬做為氫化硝基苯生成含氧偶氮苯；美國專利第4,140,719號揭示以相轉移觸媒做為氫化2,4,5-三氯硝基苯生成2,4-二氟苯胺之方法。 A method for the formation of chloroaniline by liquid hydrogenation of chloronitrobenzene. Previously, the precious metal was used as a catalyst, including palladium, platinum and rhodium. The catalyst was hydrogenated to p-chloroaniline. Hydrogenation of m-chloronitrobenzene to m-chloroaniline, Coq [J. Molecular Catalysis, Vol. 79, p. 243, 1993] The use of precious metals such as platinum and alum, to explore the size of the catalyst grain size for p-chloronitrobenzene The effect of selective hydrogenation of benzene. Figueras et al. [Applied Catalysis, Vol. 76, pp. 255-266, 1991] reveals the use of base metals as hydrogenation catalysts for p-chloronitrobenzene; Liao et al. [J.Chem.Soc ., Chem. Comm., pp. 1155-1156, 1995] reveals a palladium-ruthenium bimetallic as a hydrogenation catalyst for p-chloronitrobenzene; a paper by Vitulli et al. [Catalysis Letter, Vol. 44, p. Pp. 205-210, 1997] Reveals the hydrogenation reaction catalyst for platinum/alumina as p-chloronitrobenzene; Lin et al. [J. Molecular Catalysis A: Chemical, Vol. 159, pp. 115-120, 2000] revealed the addition of surfactant surfactant polyvinyl alcohol (polyvinylpyrrolone) on platinum metal, as a hydrogenation reaction catalyst for p-chloronitrobenzene. U.S. Patent No. 4,326,078 , the disclosure of which is incorporated herein by reference to U.S. Pat. No. 4, the disclosure of which is incorporated herein by reference. , 4-difluoroaniline method.
以貴重金屬如鉑、鈀或銠金屬做為觸媒，不但價格昂貴，而且因氫化能力太強，以致有較高的副產物；鎳金屬雖常被做為液態氫化反應觸媒，但其活性不高。自二次世界大戰前後由Schlesinger和Brown父子等人發現硼化金屬後，陸續有許多人投入硼化金屬觸媒的研究，Xie[Applied Catalysis A，第189卷，第45頁，1999年]以化學還原法製備一系列的Ni-B/SiO2非晶形觸媒，並以stearonitrile的氫化反應做測試，相較於其它以Ni為主的觸媒， 如：商用觸媒倫尼鎳(Raney Ni)，Ni-B/SiO2觸媒都顯示出有較高的活性和對一級胺有較佳的選擇性，Okamoto[J.Chem.Soc.，第75卷，第2027頁，1979年]發現NiB觸媒具有特殊的氫化活性、選擇性及耐毒特性。硼化金屬觸媒也可經由添加微量促進劑來改變催化活性或選擇性，Deng等發現添加鎢(W)於CoB觸媒中對葡萄糖之C=O鍵氫化有顯著的促劑效果[Chemistry Letter,第28卷，第629頁，1999年]，Yu等人[Applied Catalysis A：，第163卷，第1-13頁，1997年]利用化學還原法以硼氫化鉀還原含有鎳鹽跟鈷鹽的溶液，製備Ni-Co-B雙金屬合金觸媒，結果指出適度的鈷含量添加到Ni-B非晶形合金觸媒中可以增加氫化反應的活性。Lee等人[Industrial and Engineering Chemistry Research，第40卷，第1495-1499頁，2001年]揭示不同的製備環境對觸媒的表面型態、顆粒大小以及表面積都有很大的影響，而表面積的大小則是影響反應活性的主要因素。Liu等人[Industrial and Engineering Chemistry Research，第45卷，第62-69頁，2006年]揭示在298 K及充滿氮氣的環境下製備NiPB觸媒，可以得到對含氯硝基苯的氫化反應有最好活性的NiPB觸媒，並且發現反應溶劑對反應的轉化率有很大的影響，使用甲醇會比使用乙醇獲得更高的轉化率。 The use of precious metals such as platinum, palladium or rhodium as a catalyst is not only expensive, but also has a high hydrogenation capacity, resulting in higher by-products; nickel metal is often used as a liquid hydrogenation catalyst, but its activity not tall. Since the discovery of boride metals by Schlesinger and Brown and sons before and after the Second World War, many people have been investigating the use of boride metal catalysts, Xie [Applied Catalysis A, Vol. 189, p. 45, 1999]. A series of Ni-B/SiO 2 amorphous catalysts were prepared by chemical reduction method and tested by hydrogenation of stearonitrile, compared with other Ni-based catalysts, such as commercial catalyst Raney Ni. ), Ni-B/SiO 2 catalysts all show higher activity and better selectivity for primary amines, Okamoto [J. Chem. Soc., Vol. 75, p. 2027, 1979] NiB catalysts have special hydrogenation activity, selectivity and resistance to toxicity. The boron boride catalyst can also change the catalytic activity or selectivity by adding a trace promoter. Deng et al. found that the addition of tungsten (W) has a significant accelerator effect on the C=O bond hydrogenation of glucose in the CoB catalyst [Chemistry Letter , Vol. 28, p. 629, 1999], Yu et al. [Applied Catalysis A:, Vol. 163, pp. 1-13, 1997] Reduction of nickel and cobalt salts by potassium borohydride using chemical reduction The solution prepared Ni-Co-B bimetallic alloy catalyst showed that a moderate cobalt content was added to the Ni-B amorphous alloy catalyst to increase the hydrogenation activity. Lee et al. [Industrial and Engineering Chemistry Research, Vol. 40, pp. 1495-1499, 2001] revealed that different preparation environments have a large effect on the surface morphology, particle size and surface area of the catalyst, while surface area Size is the main factor affecting the reactivity. Liu et al. [Industrial and Engineering Chemistry Research, Vol. 45, pp. 62-69, 2006] revealed that the preparation of NiPB catalyst in a 298 K and nitrogen-filled environment can provide hydrogenation of chloronitrobenzene. The most active NiPB catalyst is found and the reaction solvent is found to have a large effect on the conversion of the reaction. The use of methanol results in a higher conversion than the use of ethanol.
含氯硝基苯的氫化反應其副產物非常多，一般以含氯苯胺為所希望產生的物質，以下為對氯硝基苯之反應式。 The hydrogenation reaction of chloronitrobenzene has a large number of by-products, and generally contains chloroaniline as a desired substance, and the following is a reaction formula of p-chloronitrobenzene.
本發明揭示以鉬為促進劑改質之鎳鈷硼奈米非晶態觸媒在含氯硝基苯液相氫化反應上的應用。此觸媒係以醋酸鎳、醋酸鈷及鉬酸銨為原料，先將其溶於甲醇與水的混合溶劑中(甲醇與水之體積比介於0.1至1之間)，再以硼氫化物溶液於氮氣流下還原製成奈米微粒，經離心、水洗後，即得具高催化活性之鉬-鎳鈷硼觸媒，其組成可以Moz-NiCoxBy表示，其中x為鈷與鎳之原子比，y為鈷與硼之原子比，z為鉬與鎳之原子比(0.1≦x、y、z≦1)。製備之觸媒粒徑在5奈米至100奈米之間，且為非結晶型態，比表面積介於20至100 m2/g之間。含氯硝基苯氫化反應係在一淤漿或流動式反應器進行，溶劑為四個碳以下的醇類，氫氣壓力在5至40大氣壓之間，反應溫度為40至150℃之間，此觸媒對於含氯硝基苯的氫化反應，具有高活性與高產物選擇性的特質，含氯苯胺選擇率大於98%。 The invention discloses the application of a nickel-cobalt boron nano-amorphous catalyst modified with molybdenum as a promoter in the liquid phase hydrogenation reaction of chloronitrobenzene. The catalyst is made of nickel acetate, cobalt acetate and ammonium molybdate, and is first dissolved in a mixed solvent of methanol and water (the volume ratio of methanol to water is between 0.1 and 1), followed by borohydride. The solution is reduced to a nanoparticle by a nitrogen stream. After centrifugation and water washing, a molybdenum-nickel-cobalt-boron catalyst having high catalytic activity is obtained, and its composition can be represented by Mo z -NiCo x B y , where x is cobalt and nickel. The atomic ratio, y is the atomic ratio of cobalt to boron, and z is the atomic ratio of molybdenum to nickel (0.1 ≦ x, y, z ≦ 1). The prepared catalyst has a particle size of between 5 nm and 100 nm and is of an amorphous state with a specific surface area of between 20 and 100 m 2 /g. The chloronitrobenzene hydrogenation reaction is carried out in a slurry or a mobile reactor, the solvent is an alcohol of four carbon or less, the hydrogen pressure is between 5 and 40 atm, and the reaction temperature is between 40 and 150 ° C. The catalyst has high activity and high product selectivity for the hydrogenation reaction of chloronitrobenzene, and the selectivity to chloroaniline is greater than 98%.
其中硼氫化物係硼氫化鈉或硼氫化鉀，用量為每莫耳鎳與鈷使用2至5 莫耳(硼對鎳與鈷莫耳數比為2至5)，最佳用量為每莫耳鎳與鈷的鹽使用3莫耳硼氫化物；氫化反應之溶劑為甲醇或乙醇；製備觸媒時在20至70℃之溫度；製備觸媒時以在不含氧之氣氛下製備，例如氮氣或氫氣下，滴入硼氫化物，含氯硝基苯為鄰氯硝基苯，間氯硝基苯或對氯硝基苯，其產物為鄰氯苯胺，間氯苯胺或對氯苯胺，氫化反應之氫氣壓力最佳是在5至15大氣壓，氫化反應之反應溫度是在50至100℃之間。 The borohydride is sodium borohydride or potassium borohydride in an amount of 2 to 5 per mole of nickel and cobalt. Mohr (boron to nickel to cobalt molar ratio of 2 to 5), the optimum amount is 3 moles of borohydride per mole of nickel and cobalt; hydrogenation reaction solvent is methanol or ethanol; preparation catalyst When the catalyst is prepared, the borohydride is added dropwise under an atmosphere containing no oxygen, such as nitrogen or hydrogen, and the chloronitrobenzene is o-chloronitrobenzene, m-chloronitrobenzene. The base benzene or p-chloronitrobenzene, the product of which is o-chloroaniline, m-chloroaniline or p-chloroaniline, the hydrogen pressure for hydrogenation is preferably 5 to 15 atm, and the hydrogenation reaction is at 50 to 100 ° C. between.
本發明製造之Moz-NiCoxBy合金觸媒之特性為其係黑色奈米固體微粒，粒徑介於5至100奈米之間，第二特性為應用於含氯硝基芳香族之液相氫化中具有高催化活性，能迅速將含氯硝基苯氫化成含氯苯胺。 The Mo z -NiCo x B y alloy catalyst produced by the invention has the characteristics of being black nano solid particles with a particle diameter of 5 to 100 nm, and the second characteristic is applied to a chlorine-containing nitroaromatic group. It has high catalytic activity in liquid phase hydrogenation and can rapidly hydrogenate chloronitrobenzene to chloroaniline.
本發明揭示以鉬為促進劑改質之鎳鈷硼奈米非晶態觸媒在含氯硝基苯液相氫化反應上的應用。此觸媒係以醋酸鎳、醋酸鈷及鉬酸銨為原料，先將其溶於甲醇與水的混合溶劑中(甲醇與水之體積比介於0.1至1之間)，再以硼氫化物溶液於氮氣流下還原製成奈米微粒，經離心、水洗後，即得具高催化活性之鉬-鎳鈷硼觸媒，其組成可以Moz-NiCoxBy表示，其中x為鈷與鎳之原子比，y為鈷與硼之原子比，z為鉬與鎳之原子比(0.1≦x、y、z≦1)，製備之觸媒粒徑在5奈米至100奈米之間，且為非結晶型態，比表面積介於20至100 m2/g之間。含氯硝基苯氫化反應係在一淤漿或流動式反應器進行，溶劑為四個碳以下的醇類，氫氣壓力在5至40大氣壓之間，反應溫度為40至150℃之間，此觸媒對於含氯硝基苯的氫化反應，具有高 活性與高產物選擇性的特質，含氯苯胺選擇率大於98%。 The invention discloses the application of a nickel-cobalt boron nano-amorphous catalyst modified with molybdenum as a promoter in the liquid phase hydrogenation reaction of chloronitrobenzene. The catalyst is made of nickel acetate, cobalt acetate and ammonium molybdate, and is first dissolved in a mixed solvent of methanol and water (the volume ratio of methanol to water is between 0.1 and 1), followed by borohydride. The solution is reduced to a nanoparticle by a nitrogen stream. After centrifugation and water washing, a molybdenum-nickel-cobalt-boron catalyst having high catalytic activity is obtained, and its composition can be represented by Mo z -NiCo x B y , where x is cobalt and nickel. The atomic ratio, y is the atomic ratio of cobalt to boron, z is the atomic ratio of molybdenum to nickel (0.1≦x, y, z≦1), and the prepared catalyst has a particle size of between 5 nm and 100 nm. It is an amorphous form with a specific surface area of between 20 and 100 m 2 /g. The chloronitrobenzene hydrogenation reaction is carried out in a slurry or a mobile reactor, the solvent is an alcohol of four carbon or less, the hydrogen pressure is between 5 and 40 atm, and the reaction temperature is between 40 and 150 ° C. The catalyst has high activity and high product selectivity for the hydrogenation reaction of chloronitrobenzene, and the selectivity to chloroaniline is greater than 98%.
製備NiCoB觸媒：秤取0.49974克(2毫莫耳)醋酸鎳四水合物(默克公司)與0.049814克(0.2毫莫耳)醋酸鈷四水合物(默克公司)於250ml錐形瓶中，加入10 ml去離子水和10ml甲醇(>99%)製成鎳莫耳濃度為0.1 M和鈷莫耳濃度為0.01M之溶液；再秤取0.22698克硼氫化鈉(默克公司)(硼與鎳莫耳數比為3)於燒杯中，加入3 ml去離子水和3ml甲醇製成莫耳濃度為1 M之溶液。錐形瓶置於電磁攪拌器之上，在磁石攪拌下通入40 ml/min氮氣以排除空氣，然後使用微量蠕動泵浦以2 ml/min速率將硼氫化鈉水溶液滴入鎳鈷鹽水溶液中，滴入過程會迅速產生黑色NiCoB觸媒微粒，並產生大量氫氣泡，待硼氫化鈉水溶液全部加入並不再產生氫氣泡後反應即停止。而後使用高速離心機將NiCoB觸媒自溶液中分離，以去離子水攪拌清洗三次，再以甲醇(>99%)溶液清洗三次，所得觸媒為非晶態結構(XRD分析)，粒徑為3-5 nm(TEM分析)。 Preparation of NiCoB catalyst: Weigh 0.49974 g (2 mmol) of nickel acetate tetrahydrate (Merck) and 0.049814 g (0.2 mmol) of cobalt acetate tetrahydrate (Merck) in a 250 ml Erlenmeyer flask. Add 10 ml of deionized water and 10 ml of methanol (>99%) to make a solution with a nickel molar concentration of 0.1 M and a cobalt molar concentration of 0.01 M; then weigh 0.22698 g of sodium borohydride (Merck) (boron) The molar ratio to nickel was 3). In a beaker, 3 ml of deionized water and 3 ml of methanol were added to prepare a solution having a molar concentration of 1 M. The conical flask was placed on a magnetic stirrer. Under the stirring of the magnet, 40 ml/min of nitrogen gas was introduced to remove the air, and then the aqueous sodium borohydride solution was dropped into the nickel cobalt salt aqueous solution at a rate of 2 ml/min using a micro-peristaltic pump. The dropping process rapidly generates black NiCoB catalyst particles and generates a large amount of hydrogen bubbles. When the sodium borohydride aqueous solution is completely added and hydrogen bubbles are no longer generated, the reaction stops. Then, the NiCoB catalyst was separated from the solution by a high-speed centrifuge, washed three times with deionized water, and then washed three times with a methanol (>99%) solution. The obtained catalyst was amorphous (XRD analysis), and the particle size was 3-5 nm (TEM analysis).
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供
給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
製備Mo/Ni莫耳數比為0.1之Mo-NiCoB(0.1)觸媒：製備方法同比較例1，將0.03531克鉬酸銨溶於錐形瓶之0.1 M醋酸鎳四水合物和0.01M醋酸鈷四水合物水溶液中，其後以磁石攪拌使之混合，並通入氮氣流以排除空氣；稱取硼氫化鈉0.22698克(6毫莫耳)(默克公司)，將其以3毫升去離子水與3毫升99.9%甲醇溶解。在25℃、氮氣流下，以蠕動泵浦將硼氫化鈉水溶液緩慢滴入錐形瓶中，在持續攪拌下即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以99.9%甲醇洗滌3次。 Preparation of Mo-NiCoB (0.1) catalyst with Mo/Ni molar ratio of 0.1: Preparation method Compared with Comparative Example 1, 0.03531 g of ammonium molybdate was dissolved in a conical flask of 0.1 M nickel acetate tetrahydrate and 0.01 M acetic acid. In an aqueous solution of cobalt tetrahydrate, it is then stirred with a magnet to mix it, and a nitrogen stream is passed to remove the air; 0.225698 g (6 mmol) of sodium borohydride (Merke) is weighed and taken to 3 ml. Ionic water was dissolved in 3 ml of 99.9% methanol. The aqueous solution of sodium borohydride was slowly dripped into the Erlenmeyer flask by peristaltic pumping at 25 ° C under a nitrogen flow, and a black catalyst was formed under continuous stirring; after the catalyst was washed 3 times with deionized water, 99.9% was further washed. Wash with methanol 3 times.
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，
填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
製備Mo/Ni莫耳數比為0.2之Mo-NiCoB(0.2)觸媒：製備方法同比較例1，將0.07062克鉬酸銨溶於錐形瓶之0.1 M醋酸鎳四水合物和0.01M醋酸鈷四水合物水溶液中，其後以磁石攪拌使之混合，並通入氮氣流以排除空氣；稱取硼氫化鈉0.22698克(6毫莫耳)(默克公司)，將其以3毫升去離子水與3毫升99.9%甲醇溶解。在25℃、氮氣流下，以蠕動泵浦將硼氫化鈉水溶液緩慢滴入錐形瓶中，在持續攪拌下即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以99.9%甲醇洗滌3次。 Preparation of Mo-NiCoB (0.2) catalyst with Mo/Ni molar ratio of 0.2: Preparation method Compared with Comparative Example 1, 0.07062 g of ammonium molybdate was dissolved in an Erlenmeyer flask of 0.1 M nickel acetate tetrahydrate and 0.01 M acetic acid. In an aqueous solution of cobalt tetrahydrate, it is then stirred with a magnet to mix it, and a nitrogen stream is passed to remove the air; 0.225698 g (6 mmol) of sodium borohydride (Merke) is weighed and taken to 3 ml. Ionic water was dissolved in 3 ml of 99.9% methanol. The aqueous solution of sodium borohydride was slowly dripped into the Erlenmeyer flask by peristaltic pumping at 25 ° C under a nitrogen flow, and a black catalyst was formed under continuous stirring; after the catalyst was washed 3 times with deionized water, 99.9% was further washed. Wash with methanol 3 times.
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
製備Mo/Ni莫耳數比為0.3之Mo-NiCoB(0.3)觸媒：製備方法同比較例1，將0.10593克鉬酸銨溶於錐形瓶之0.1 M醋酸鎳四水合物和0.01M醋酸鈷四水合物水溶液中，其後以磁石攪拌使之混合，並通入氮氣流以排除空氣；稱取硼氫化鈉0.22698克(6毫莫耳)(默克公司)，將其以3毫升去離子水與3毫升99.9%甲醇溶解。在25℃、氮氣流下，以蠕動泵浦將硼氫化鈉水溶液緩慢滴入錐形瓶中，在持續攪拌下即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以99.9%甲醇洗滌3次。 Preparation of Mo-NiCoB (0.3) catalyst with Mo/Ni molar ratio of 0.3: Preparation method Same as Comparative Example 1, 0.10593 g of ammonium molybdate dissolved in a Erlenmeyer flask of 0.1 M nickel acetate tetrahydrate and 0.01 M acetic acid In an aqueous solution of cobalt tetrahydrate, it is then stirred with a magnet to mix it, and a nitrogen stream is passed to remove the air; 0.225698 g (6 mmol) of sodium borohydride (Merke) is weighed and taken to 3 ml. Ionic water was dissolved in 3 ml of 99.9% methanol. The aqueous solution of sodium borohydride was slowly dripped into the Erlenmeyer flask by peristaltic pumping at 25 ° C under a nitrogen flow, and a black catalyst was formed under continuous stirring; after the catalyst was washed 3 times with deionized water, 99.9% was further washed. Wash with methanol 3 times.
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
製備Mo/Ni莫耳數比為0.5之Mo-NiCoB(0.5)觸媒：製備方法同比較例1，將0.17655克鉬酸銨溶於錐形瓶之0.1 M醋酸鎳四水合物和0.01M醋酸鈷四水合物水溶液中，其後以磁石攪拌使之混合，並通入氮氣流以排除空氣；稱取硼氫化鈉0.22698克(6毫莫耳)(默克公司)，將其以3毫升去離子水與3毫升99.9%甲醇溶解。在25℃、氮氣流下，以蠕動泵浦將硼氫化鈉水溶液緩慢滴入錐形瓶中，在持續攪拌下即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以99.9%甲醇洗滌3次。 Preparation of Mo-NiCoB (0.5) catalyst with Mo/Ni molar ratio of 0.5: Preparation method Same as Comparative Example 1, 0.17655 g of ammonium molybdate dissolved in an Erlenmeyer flask of 0.1 M nickel acetate tetrahydrate and 0.01 M acetic acid In an aqueous solution of cobalt tetrahydrate, it is then stirred with a magnet to mix it, and a nitrogen stream is passed to remove the air; 0.225698 g (6 mmol) of sodium borohydride (Merke) is weighed and taken to 3 ml. Ionic water was dissolved in 3 ml of 99.9% methanol. The aqueous solution of sodium borohydride was slowly dripped into the Erlenmeyer flask by peristaltic pumping at 25 ° C under a nitrogen flow, and a black catalyst was formed under continuous stirring; after the catalyst was washed 3 times with deionized water, 99.9% was further washed. Wash with methanol 3 times.
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
製備Mo/Ni莫耳數比為0.6之Mo-NiCoB(0.6)觸媒：製備方法同比較例 1，將0.21186克鉬酸銨溶於錐形瓶之0.1 M醋酸鎳四水合物和0.01M醋酸鈷四水合物水溶液中，其後以磁石攪拌使之混合，並通入氮氣流以排除空氣；稱取硼氫化鈉0.22698克(6毫莫耳)(默克公司)，將其以3毫升去離子水與3毫升99.9%甲醇溶解。在25℃、氮氣流下，以蠕動泵浦將硼氫化鈉水溶液緩慢滴入錐形瓶中，在持續攪拌下即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以99.9%甲醇洗滌3次。 Preparation of Mo-NiCoB (0.6) catalyst with Mo/Ni molar ratio of 0.6: preparation method and comparative example 1. Dissolving 0.21186 g of ammonium molybdate in 0.1 M nickel acetate tetrahydrate and 0.01 M cobalt acetate tetrahydrate aqueous solution in an Erlenmeyer flask, followed by mixing with a magnet and passing a nitrogen stream to remove air; 0.22698 g (6 mmol) of sodium borohydride (Merck) was weighed and dissolved in 3 ml of deionized water and 3 ml of 99.9% methanol. The aqueous solution of sodium borohydride was slowly dripped into the Erlenmeyer flask by peristaltic pumping at 25 ° C under a nitrogen flow, and a black catalyst was formed under continuous stirring; after the catalyst was washed 3 times with deionized water, 99.9% was further washed. Wash with methanol 3 times.
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
製備Mo/Ni莫耳數比為1之Mo-NiCoB(1)觸媒：製備方法同比較例1，將0.3531克鉬酸銨溶於錐形瓶之0.1 M醋酸鎳四水合物和0.01M醋酸鈷四水 合物水溶液中，其後以磁石攪拌使之混合，並通入氮氣流以排除空氣；稱取硼氫化鈉0.22698克(6毫莫耳)(默克公司)，將其以3毫升去離子水與3毫升99.9%甲醇溶解。在25℃、氮氣流下，以蠕動泵浦將硼氫化鈉水溶液緩慢滴入錐形瓶中，在持續攪拌下即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以99.9%甲醇洗滌3次。 Preparation of Mo-NiCoB (1) catalyst with Mo/Ni molar ratio of 1: Preparation method Same as Comparative Example 1, 0.3531 g of ammonium molybdate dissolved in Erlenmeyer flasks of 0.1 M nickel acetate tetrahydrate and 0.01 M acetic acid Cobalt water In the aqueous solution, the mixture was stirred with a magnet and passed through a stream of nitrogen to remove air; 0.225698 g (6 mmol) of sodium borohydride (Merke) was weighed and 3 ml of deionized water was used. Dissolved with 3 ml of 99.9% methanol. The aqueous solution of sodium borohydride was slowly dripped into the Erlenmeyer flask by peristaltic pumping at 25 ° C under a nitrogen flow, and a black catalyst was formed under continuous stirring; after the catalyst was washed 3 times with deionized water, 99.9% was further washed. Wash with methanol 3 times.
將製備之觸媒與2.54克的對氯硝基苯、80毫升甲醇置於反應器內；在反應系統內通入氫氣流10分鐘，以除去系統內的空氣；後以低速攪拌(約150 rpm)，並升溫至反應溫度80℃，同時逐步加壓至反應壓力160 psig；待溫度與壓力達到反應條件時，增加攪拌速度至500 rpm，此時定為反應開始時刻(t=0)；以10分鐘為區間取樣一次，取樣時先溢流約10滴之樣品液，以排除取樣管中前批樣品液殘留所造成之誤差；反應完畢後，停止氫氣供給，並依次降溫、降壓；將樣品以氣相色層分析儀(中國層析8700 F)分析反應物與產物濃度，分析之層析管柱為3公尺長，直徑1/8英吋之不鏽鋼管，填充物為5% OV-101/80-100 mesh Chromosorb WAW-DMSC。反應結果如下：
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