200902147 九、發明說明： 【發明所屬之技術領域】 本^月係#製造尚分子穩定化錄與姑奈求合金觸媒的方法及其應 用尤才曰種於水洛液中以硼氫化鈉為還原劑經化學還原法還原含水溶性 有機高分子之_和紐混合物製造高分子歡⑽無合金觸媒的方 法’並聽鹵素硝基料族如職雜苯之油氫化反應。 ’T、米科技研發潛力絲，被視為廿—世紀科技與產紐展的最大驅動 力7日的科子小自原子、大至物體的性質我們都可以清楚的瞭解。但 #^tf^A^(mes〇.scaleWm(cluster) , ，現在則仍 在探索階段；奈米物質的性質異於原子規模，也與一般物質不大相同，在 奈米尺度下，物質會呈現避異於巨觀尺度下的物理、化學及生物性質，材 料將因產生完全不同的特㈣形成特殊功能。 、奈米物質隨不同領域有不同的絲，對觸媒而言，當觸媒的粒徑逐漸 咸J才八催化! 生貝亦隨之改變。一般而言，粒徑介於卜⑽奈米之間時， 其催化性質與錄雛有顯著的差異，_為奈米觸；其實在較早之前 觸媒已經是奈米的等級，只是以超微細觸媒稱之。隨著奈料料的研究曰 益蓬勃，有關奈米觸媒的定義亦日見混亂，但主要有下列幾種。依顆粒直 徑定義—顆粒直徑小於⑽奈米的稱為奈米觸媒；依孔洞直徑定義—觸媒 均為多孔_ ’故有人將孔__級，尤其_、於Μ奈米的稱 為奈米觸媒，例如•的孔喊徑均騎米級，故《人稱其為奈米材料· 200902147 依孔洞管壁厚度定義’也有人將觸麻壁厚度在奈米級的稱為奈米觸媒， 亦稱為奈米結構觸媒。 超細非晶(amorphous)合金粒子由於其本質上許多特殊的特性，因而引 起多方的注意’例如：姉鱗(shGrt_rangeG刪、絲有郭。ng r等 ―)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。 這個結合了非晶形及超細合金的粒子，具有i.高表面不飽和活性位置，2 (、具有結晶缺陷，3.等方性(i論_ _敝)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。 本研究所用賴職在石化卫業上已經廣泛的使用，如未飽和有機物 的氳化 '加氫裂解、合成氣甲烧化及水蒸氣重組料。不過傳統的義媒 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。本發明係有關含氣硝基苯在含有高分子穩定化錄钻合金觸媒 存在下與氣氣反應生成對氣苯胺之製程，將其溶於含水溶性有機高分子 {)聚乙稀吡略酮之水溶液中，此含有鎳、銘與高分子聚乙稀吡咯酮的觸媒係 以鎳的鹽類加讀之魏並與高分子pvp混合，並闕氫化物作為還原劑 製備而成，其組成可以用PVP-NiC〇xBy表示，PVP與鎳之莫耳比為〇.卜邡， X為鈷與鎳之莫耳比，y為硼與鎳之莫耳比，X之範圍為〇.〇1 g x $ i， y之範圍為〇· 〇1 $ y $ 1 ,此Nic〇;^y為奈米級顆粒，其顆粒直徑皆在5〇 不米以下，且為非結晶型態，比表面積大於5 m2/g。氫化反應係在一於漿 反應器進行’溶劑為四個碳以下的醇類，氫氣壓力在5 - 40大氣壓之間， 反應溫度為40 - 150 °c之間。此觸媒對於含氯硝基苯的氫化反應，具有高 200902147 活性與高產物選擇性的特皙，豆 啊資其產物有99 %以上均是含氯苯胺。 【先前技術】 不米金屬U粒因具南表面原子數，表面粗麵度隨粒徑減小而增加， 开v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 與金屬原子之娜化學與物雌f，使其倍受學術界及產業㈣目。製備 金屬奈紐粒的技财化學還縣、電化學還縣、氣概積法、微波轄 射法、i外線光解法、熱分解法等，其巾化學還原賴具有容易製備、分 散穩定、粒徑較小及分佈較窄的優.點，在催化應用上廣被使用，含氯破基 本以液態氫化反應生成含氣苯胺的方法，先前技藝均是以貴重金屬為觸 媒，其包括鈀、鉑及釕三種觸媒，用為對氯硝基苯氢化成對氣苯胺，間氯 硝基笨氢化成間氯苯胺，Coq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[j. Molecular Catalysis，第79卷，第 243 頁，1993 年]。’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氢化反應觸媒；Liao等人之論 文[J_ Chem_ Soc.，Chem_ Comm”第 1155-1156 頁,1995 年]揭示以把-釕雙金屬 做為對氯硝基苯之氢化反應觸媒；Vitulli等人之論文[Catalysis Letter，第44 卷，第205-210頁，1997年]揭示以鉑/氧化鋁為對氣硝基苯之氢化反應觸媒；200902147 IX. Description of the invention: [Technical field to which the invention belongs] This method of manufacturing the molecular stabilization and the alloy catalyst of Gu Nai and its application, especially in the water solution, with sodium borohydride The reducing agent is subjected to a chemical reduction method to reduce a mixture of a water-soluble organic polymer and a mixture of a mixture of a water-soluble organic polymer to produce a polymer (10) alloy-free catalyst, and to listen to a hydrogenation reaction of a halogen nitro group such as a benzene oil. 'T, rice technology research and development potential silk, is regarded as the biggest driving force of the century-century technology and production exhibition. We can clearly understand the nature of the small-scale atomic and large objects on the 7th. But #^tf^A^(mes〇.scaleWm(cluster), , is still in the exploration stage; the nature of nanomaterials is different from the atomic scale, and it is not the same as the general material. At the nanometer scale, the material will The physics, chemical and biological properties under the macroscopic scale are avoided, and the materials will form special functions due to the creation of completely different specialties. The nanomaterials have different filaments in different fields, and the catalysts are catalysts. The particle size gradually becomes salty and J-catalyzed! The raw shellfish also changes. Generally speaking, when the particle size is between (10) nanometers, the catalytic properties are significantly different from those of the recorded chicks, _ is the nano-touch; In the early days, the catalyst was already in the grade of nanometer, but it was called ultra-fine catalyst. With the research of naphthalene materials, the definition of nanocatalyst is also chaotic, but mainly the following According to the particle diameter definition - the particle diameter is less than (10) nanometer called nanocatalyst; according to the pore diameter definition - the catalyst is porous _ 'so someone will hole __ grade, especially _, in the name of Μ奈米For the nanocatalyst, for example, the hole of the hole is called the meter level, so "people call it Rice material · 200902147 According to the thickness definition of the hole wall of the hole, there is also a nano-scale called nano-catalyst, which is also called nano-structure catalyst. Ultra-fine amorphous alloy particles due to its In essence, there are many special characteristics, which cause a lot of attention 'for example: scales (shGrt_rangeG, silk, Guo, ng r, etc.) and high dispersion, they have great potential in powder metallurgy, magnetic materials, and catalysts. This combination of amorphous and ultra-fine alloy particles has i. high surface unsaturated active sites, 2 (with crystal defects, 3. isotropic (i _ _ 敝) structure, making it specific to The reaction has high activity, high selectivity and high stability. The research has been widely used in the petrochemical industry, such as the desulfurization of unsaturated organic compounds, hydrocracking, syngas, and steam reforming. However, the traditional medium is likely to cause activity degradation due to the sintering of the pores of the carrier, or the reactants remain on the active group. The present invention relates to a gas-containing nitrobenzene containing a polymer stabilized recording alloy catalyst. In the presence of a reaction with gas to form a gas aniline, it is dissolved in an aqueous solution containing a water-soluble organic polymer {) polyethylpyrrolidone, which contains a catalyst of nickel, high molecular weight polypyrrrolone It is prepared by mixing the salt of nickel with the polymer pvp and preparing the hydride as a reducing agent. The composition can be expressed by PVP-NiC〇xBy, and the molar ratio of PVP to nickel is 〇.邡, X is the molar ratio of cobalt to nickel, y is the molar ratio of boron to nickel, X ranges from 〇.〇1 gx $ i, y ranges from 〇· 〇1 $ y $ 1 , this Nic〇 ;^y is a nano-sized particle with a particle diameter of less than 5 〇 2 m and an amorphous state with a specific surface area greater than 5 m 2 /g. The hydrogenation reaction is carried out in a slurry reactor with four solvents. Alcohols below carbon, hydrogen pressure between 5 and 40 atmospheres, and reaction temperatures between 40 and 150 °c. The catalyst has a high activity of 200902147 and high product selectivity for the hydrogenation reaction of chloronitrobenzene, and more than 99% of the products of the bean are chloroaniline. [Prior Art] Because of the atomic number of the south surface of the non-rice metal U, the surface roughness increases with the decrease of the particle size, and the open-v is an uneven atomic step, which increases the chemical reaction contact surface and is different from the block shape. Metal and metal atomic chemistry and material f, making it subject to academic and industrial (four). The chemical chemistry of the preparation of the metal nai particles is also the county, the electrochemical county, the gas accumulation method, the microwave ray ray method, the i-external photolysis method, the thermal decomposition method, etc., and the chemical reduction of the towel has an easy preparation, dispersion stability, and particle size. The smaller and narrower distribution points are widely used in catalytic applications. The chlorine-containing method is basically a liquid hydrogenation reaction to form a gas-containing aniline. The prior art is based on precious metals, including palladium and platinum. And three kinds of catalysts, which are used to hydrogenate p-chloronitrobenzene to p-aniline, m-chloronitrobenzene to m-chloroaniline, Coq to platinum and ruthenium and other precious metals, to investigate the size of the catalyst grain for p-chloro Effect of selective hydrogenation of nitrobenzene [j. Molecular Catalysis, Vol. 79, p. 243, 1993]. 'The paper by Figueras et al. [Applied Catalysis, Vol. 76, pp. 255-266, 1991] reveals the use of base metals as a catalyst for the hydrogenation of p-chloronitrobenzene; a paper by Liao et al. [J_Chem_Soc. , Chem_Comm, pp. 1155-1156, 1995] discloses the use of a ruthenium bimetallic as a hydrogenation catalyst for p-chloronitrobenzene; a paper by Vitulli et al. [Catalysis Letter, Vol. 44, pp. 205-210 Page, 1997] reveals a catalyst for the hydrogenation of p-nitrobenzene with platinum/alumina;
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 (聚乙稀°比略酮）在鉑金屬 200902147 上’做為對氣硝基苯之氛化反應觸媒。美國專利第4,326,078號，揭示以貴 重金屬做為氢化硝基苯生成含氧偶氮苯；美國專利第4，14〇,719號揭示以相 轉移觸媒做為氟化2,4,5-三氯硝基苯生成2,4-二氟苯胺之方法。以貴重金屬 如銘、把或姥金屬做為觸媒’不但價值昂貴，而且因氢化能力太強，以致 有較南的副產物；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 續有許多專家、學者投入硼化金屬觸媒的研究行列，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/Si02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/Si02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於1979年發表論文[J. Chem. Soc.,第75卷, 第2027頁,1979年]’以XPS分析P-lNiB觸媒的表面原子狀態，解釋NiB 觸媒具有特殊的氳化活性、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=0鍵氫化有顯著的促劍效果[Chemistry Letter，第28卷， 第 629 頁，1999 年]，Yu 等人[AppliedCatalysis 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 200902147 面型態、齡大似及表面積都雜辟，絲_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61 2 3_69頁，2〇〇6年]揭示在298 K及充滿氮氣的環境下製 備ΝιΡΒ觸媒，可以得到對含氣硝基苯的氫化反應有最好活性的NipB觸媒， 並且s登明反應媒介物對反應的轉化率有很大的影響，使用曱醇會比使用乙 醇獲得更高的轉化率。 含氣硝基苯的氫化反應可以用下列反應式表示，其副產物非常多，一 般以含氣苯胺為所希望產生的物質。Lin et al. [J. Molecular Catalysis A: Chemical, Vol. 159, pp. 115-120, 2000] reveals the addition of the surfactant polyvinyl alcohol (polyethylene ketone) on platinum metal 200902147 It is a catalyst for the reaction of nitrobenzene. 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. A method of producing chloronitrobenzene to produce 2,4-difluoroaniline. The use of precious metals such as Ming, ruthenium or ruthenium as a catalyst is not only expensive, but also has a relatively strong hydrogenation capacity, so that it has a relatively southern by-product; although nickel metal is often used as a liquid hydrogenation catalyst, its activity not tall. Since the discovery of boride metals by Schlesinger and Brown and his sons before and after the Second World War, many experts and scholars have been investing in the research of boride metal catalysts, xie [Applied Catalysis A, Vol. 189, p. 45, 1999. A series of Ni-B/SiO2 amorphous catalysts were prepared by chemical reduction method and tested by hydrogenation of stearonitrile, compared with other Ni-based catalysts, such as: commercial catalyst ronic nickel ( Raney Ni), Ni-B/Si02 catalysts have shown higher activity and better selectivity for primary amines. Okamoto published a paper in 1979 [J. Chem. Soc., Vol. 75, No. 2027 Page, 1979] 'Analysis of the surface atomic state of P-lNiB catalyst by XPS, explaining that NiB catalyst has special deuteration activity, selectivity and toxicity resistance. 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 sword-stimulating effect on the C=0 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 was used to prepare a Ni-Co-B bimetallic alloy catalyst. The results indicate that a moderate cobalt content can be 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] reveals that different preparation environments for the catalyst table 200002147 are superficial, age-like and surface area are all mixed, silk_ Size is the main factor affecting the reactivity. Liu et al. [industrial and Engineering Chemistry Research, Vol. 45, pp. 61 2 3_69, 2〇〇6 years] revealed that ΝιΡΒ catalyst can be prepared in a 298 K and nitrogen-filled environment to obtain gas-containing nitrobenzene. The hydrogenation reaction has the most active NipB catalyst, and the simon reaction vehicle has a large effect on the conversion of the reaction, and the use of decyl alcohol will result in higher conversion than the use of ethanol. The hydrogenation reaction of the gas-containing nitrobenzene can be represented by the following reaction formula, which has a large number of by-products, and generally contains a gas-containing aniline as a desired substance.
美國專利有關含氣石肖基本虱化反應製程’有下列與本案有關之專利. 1 7,091,383 T Method for the production of amines 2 7,064,237 T Method for the production of amines 3 6,894,193 T Method for hydrogenating liquid organic compounds 200902147 4 6,815,562 Τ Process for the preparation of nitrodiphenylamines 5 6,469,181 T Process for preparing 2-oxindoles and N-hvdroxv-2-oxindoles 6 6,350,911 T Method for producing amines 7 6,316,381 T Multimetallic catalyst and process for preparing substituted aromatic amines 8 6,197,716 T Process for the production of aromatic halogen-amino compounds 9 5,977,411 T Catalytic hvdrogeneration of nitrobenzene to 4-aminodiphenylamine in the presence of a hydroxyl compound and a solvent 10 5,962,741 F Process for the production of aromatic halogen-amino compounds 11 5,545,754 T Process for the preparation of p-amino-phenols 12 5,304,680 T Process for the preparation of aromatic amines which are substituted by C.sub.l -C.sub.4 -alkoxv in the p-position 13 5,302,742 Mi Process for the preparation of N-acvlated p-amino-phenolsU.S. Patent No. 2,091,383 T Method for the production of amines 3,894,237 T Method for the production of amines 3,894,193 T Method for hydrogenating liquid organic compounds 200902147 4 Process for the preparation of nitrodiphenylamines 5 6,469,181 T Process for preparing 2-oxindoles and N-hvdroxv-2-oxindoles 6 6,350,911 T Method for producing amines 7 6,316,381 T Multimetallic catalyst and process for preparing substituted aromatic amines 8 6,197,716 T Process for the Production of aromatic halogen-amino compounds 9 5,977,411 T Catalytic hvdrogeneration of nitrobenzene to 4-aminodiphenylamine in the presence of a hydroxyl compound and a solvent 10 5,962,741 F Process for the production of aromatic halogen-amino compounds 11 5,545,754 T Process for the preparation of p -amino-phenols 12 5,304,680 T Process for the preparation of aromatic amines which are substituted by C.sub.l -C.sub.4 -alkoxv In the p-position 13 5,302,742 Mi Process for the preparation of N-acvlated p-amino-phenols
ϋ 14 5,126,485 M Process for the hydrogenation of halogenonitro-aromatic compounds in the presence of a sulfur-containing compound 15 5,068,436 W Hydrogenation of halonitrobenzenes without dehalogenation 16 4,625,062 T Process for producing 4-alkoxvanilines 17 4,551,551 T Preparation of bis(aminophenvl) ethers from (N-acetvl)aminophenols or their phenolates 18 4,539,428 ^ Preparation of diaminodiphenvl ethers 19 4,535,162 11 Process for catalytically reducing nitroaromatic compounds 20 4,375,550 T Hydrogenation of halogen-substituted aromatic nitro compounds 21 4,326,081 T Conversion of mononitro aromatic compounds to amino compounds bv hydrogen sulfide 22 4,326,078 T Process for preparation of hvdrazobenzenes by catalytic hydrogenation of nitrobenzenes 23 4,287,365 T Reduction of aromatic nitro compounds with Raney nickel catalyst 24 4,264,526 T Borate reduction of nitrophenols 25 4,230,637 T Process for the preparation of chlorine-substituted aromatic amines 26 4,217,307 T Process for the preparation of 2,2'-dichloro-hvdrazobenzene 27 4,212,824 ΙΠ Hydrogenation catalyst with improved metallic distribution, its preparation and use for the reduction of aromatic nitro compounds 28 4,185,036 11 Hydrogenation of mixed aromatic nitrobodies 29 4J4QJ19 ii Solid-liquid phase transfer catalysis improved method of preparing 2,4-difluoroaniline 30 4,070,401 T Method for the preparation of a halogenated aromatic amine 31 4,059,627 T Chlorinated aromatic amines 32 3,989,756 T Process for the production of halogenated aromatic primary amines 33 3,947,480 ff Dinitro- and diamino arylene disulfbnes 11 200902147 34194^717 T Process for the production of a catalyst comprisinp a novel metal carbon 35 3,933,829 T 4-Aminoauinoline derivatives 已公開之專利及文獻中，未有如本發明使用鎳钻删之奈米合金觸媒用 於含氯硝基苯氫化反應。 【發明内容】ϋ 14 5,126,485 M Process for the hydrogenation of halogenonitro-aromatic compounds in the presence of a sulfur-containing compound 15 5,068,436 W Hydrogenation of halonitrobenzenes without dehalogenation 16 4,625,062 T Process for producing 4-alkoxvanilines 17 4,551,551 T Preparation of bis(aminophenvl) ethers from (N-acetvl)aminophenols or their phenolates 18 4,539,428 ^ Preparation of diaminodiphenvl ethers 19 4,535,162 11 Process for catalytically reducing nitroaromatic compounds 20 4,375,550 T Hydrogenation of halogen-substituted aromatic nitro compounds 21 4,326,081 T Conversion of mononitro aromatic compounds to amino compounds bv hydrogen sulfide 22 4,326,078 T Reduction of aromatic nitro compounds with Raney nickel catalyst 24 4,264,526 T Borate reduction of nitrophenols 25 4,230,637 T Process for the preparation of chlorine-substituted aromatic amines 26 4,217,307 T Process f Or the preparation of 2,2'-dichloro-hvdrazobenzene 27 4,212,824 ΙΠ Hydrogenation catalyst with improved metallic distribution, its preparation and use for the reduction of aromatic nitro compounds 28 4,185,036 11 Hydrogenation of mixed aromatic nitrobodies 29 4J4QJ19 ii Solid-liquid phase transfer catalysis Improved method of preparing 2,4-difluoroaniline 30 4,070,401 T Method for the preparation of a halogenated aromatic amine 31 4,059,627 T Chlorinated aromatic amines 32 3,989,756 T Process for the production of halogenated aromatic primary amines 33 3,947,480 ff Dinitro- and diamino arylene disulfbnes 11 200902147 34194^717 T Process for the production of a catalyst comprisinp a novel metal carbon 35 3,933,829 T 4-Aminoauinoline derivatives In the published patents and documents, there is no use of nickel-bored nano-alloy catalysts for chlorine-containing nitrates as in the present invention. Hydrogenation of benzene. [Summary of the Invention]
0 本發明係有關含氣硝基苯在含有高分子穩定化鎳鈷合金觸媒存在下與 氫氣反應生成對鮮胺之製程，此含有高分子敎化鎳錢_媒係以錄 的鹽類加入含有鈷之鹽類並與溶有聚乙烯吡咯酮高分子之溶液混合，並以 删氫化物作為縣劑製備而成，其峨可_ pvp_Ni⑽表示，pw與錄 之莫耳比為G. 1-2G，X為0)與錄之莫耳比，y _與錄之莫耳比，X之範 圍為〇·oh x $丨’ y之範圍為請$ y q，此pvp—NiMy為奈 来級顆粒餘’其顆粒直徑妹5Q奈米以下，且其為非結晶聽，比表面 積大於5心，氫化反應係在-㈣反絲進行，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4〇幻5〇之間。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，豆 產物有99 上均是含《胺。本__私方轉備含有高分子歡 化錄無_媒，水雜錢高分子作為觸聽_，(简 為佳，其平均分子量之範圍介於8，_錢咖之間以1〇，鶴至4〇 _ 間者為佳，其用量為每莫耳鎳鹽水合物使用_莫耳pvp(簡錄莫耳數 比為莫耳數算法以—個PVP單體為單位，較佳曝每莫耳錄鹽 水合物使用〇·1_1〇莫耳ργρ。 驗_氫化鈉用量為每莫耳鎳無使用2_5莫耳㈣_無莫耳數比 12 200902147 為2分最佳用量為每莫耳鎳與始的鹽使用3莫耳领氨化納。勵B合金 顆粒直徑在奈_，表_大，而_非__，此觸媒對於 含氯硝絲的躲絲，財高滩與高趟着性㈣質，《其產物 有99 %以上均是含鮮胺。射臟化婦鐵化_鐵统氫化反應 之溶劑以甲醇或乙醇為最佳；製備娜_在2()至肌之溫度為最佳；製 備觸媒時財不含氧之氣氛下製備，例滅氣或域下，滴人魏化物為 最佳；含Μ基苯為間㈣基苯或對氯硝基苯，其產物為間氯苯胺或對氯0 The invention relates to a process for reacting gas-containing nitrobenzene with hydrogen in the presence of a polymer-stabilized nickel-cobalt alloy catalyst to form a crude amine, which comprises a polymerized nickel-deposited nickel-based medium added to the recorded salt. The salt containing cobalt is mixed with a solution of a polyvinylpyrrolidone polymer and prepared by using a hydride as a prefecture. The 峨p_pvp_Ni(10) indicates that the ratio of pw to the recorded molar ratio is G. 2G, X is 0) and recorded Moh ratio, y _ and recorded Mo Er ratio, X range is 〇·oh x $丨' y range is please $ yq, this pvp-NiMy is Nailai granule I' the particle diameter is less than 5Q nanometers, and it is amorphous, the specific surface area is greater than 5 hearts, the hydrogenation reaction is carried out in the - (4) reverse wire, and the solvent is alcohol below 4 carbons. The hydrogen pressure is 5 to 40. The reaction temperature between atmospheric pressure is between 4 〇 〇 5 。. The catalyst has high activity and high product selectivity for the hydrogenation reaction of chloronitrobenzene, and the bean product contains "amine" on 99. This __ private party has a polymer containing no _ media, water miscellaneous polymer as a touch _, (Jian is good, its average molecular weight range is 8, _ money between 1 钱, Hezhi 4〇_ is better, the amount is _mole pvp per mole of nickel salt hydrate (the simple molar ratio is the number of moles algorithm - a unit of PVP monomer, preferably exposed Moer's salt hydrate uses 〇·1_1〇莫耳ργρ. Test_Sodium hydride is used per mole of nickel without use 2_5 moles (4) _ no molar ratio 12 200902147 is 2 points optimal amount per mole nickel The salt used in the beginning is 3 moles of ammoniated sodium. The diameter of the alloy B is in the form of Na, _ large, and _ non __, this catalyst for the chlorinated nitrins, Cai Gaotan and Gaochun (4) quality, "more than 99% of its products are containing fresh amines. Shooting dirty fertilization _ iron-hydrogenation solvent is best methanol or ethanol; preparation of _ at 2 () to muscle temperature It is best; when preparing the catalyst, it is prepared under the atmosphere of no oxygen, such as gas or sub-domain, and the human extract is the best; the mercapto-containing benzene is m-(di)benzene or p-chloronitrobenzene, and its product Is m-chloroaniline or Chlorine
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 最佳是在50至l〇〇°C之間。 • 本發明製造之高分子穩定化NiCoB合金觸媒之概為其係黑色奈米固 體微粒’粒徑介於3-5 nm之間，第二特性為應用於鹵素頌基芳香族之液相 氫化中具有高催化活性，能迅速將對氯石肖基苯氫化成對氣苯胺。 高分子穩定化鎳與鈷合金觸媒應用於對氣硝基笨氫化成對氣苯胺反應 之主要裝置為不銹鋼電磁攪拌式高壓反應釜，採半批式操作，反應器内總 j 壓藉氫氣鋼瓶出口之壓力調節閥控制並維持於恆壓，步驟為先將製備完成 的新鮮PVP-Ni C〇xBy觸媒以反應溶劑沖入反應器内並加入反應物，在大氣壓 力下以30-60ml/min氫氣沖流10-20分鐘趕走反應器内之空氣，於ι〇〇_2〇〇 rpm低速授拌下緩慢升溫至反應溫度5〇_1〇〇。(3，然後通氳氣加壓至反應壓 力5至15大氣壓，調高攪拌速率為300-700 rpm，開始反應。 13 200902147 【實施方式】 比較例1 ·· 製備鎳與鈷觸媒NicoB,稱取ο··74克(2毫莫耳)醋酸錦四水合物(默 克λ司)和0.0498Μ克(〇.2毫莫耳)醋酸姑四水合物(默克公司)於25_平底 錐^/瓶中’加人10ml去離子水和1GmJ f醇(>99%)娜賴莫耳濃度為〇1 Μ和鈷莫耳濃度為α〇1Μ之溶液，再稱取Q.助克喊化鈉(默克公司）(删 與鎳莫耳數比為3)於燒杯中’加入3河去離子水和3ml甲醇調配成莫耳濃 度為1 Μ之，谷液’錐形瓶於電磁勝器磁石授拌下通入*而驗氮氣以排 除二氣’紐使用微魏綠以2 ml/min速轉喊化鈉水雜逐滴滴入 鎳鹽水溶液巾，滴人過程會迅速產生黑色Ni⑽觸微粒，並產生大量氮 乳泡’侧氫化鈉水溶液全部加人並不再產生氫氣泡後反應即停止，使用 高速離心機將NiCoB觸媒自溶财分離出，以去離子水麟清洗三次，再 以曱醇(>99%)溶液清洗二次，所得觸媒為非晶態結構(XRD分析），粒徑為 3-5 nm(TEM 分析）。 實施例1 : 製備PVP/Ni莫耳數比為〇_25之高分子穩定化鎳與鈷觸 PVP-NiCoB(0.25) ’莫耳數算法以一個pvp單體為單位，製備方法同比較例 1 ’於0.1 Μ醋酸鎳四水合物和醋酸銘四水合物水溶液中先溶入ο.。〗％克平 均分子量為10,000之聚乙烯吡咯鲖，稱取硼氫化鈉0 227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；在氮氣下，在 14 200902147 25°C將醋酸鎳水溶液放於錐形瓶内，以磁石_混合之，再辑動栗浦缓 慢滴入删氫化鈉水溶液，即生成黑色觸媒；將觸媒以去離子水洗務3次後， 再以99.9 %甲醇洗滌2次。 實施例2 : 製備PVP/Ni莫耳數比為i之高分子穩定化錄與姑觸 PVP-NiCoB(l)， 莫耳數算法以一個PVP單體為單位，製備方法同比較例工，於〇 ι Μ醋酸 鎳四水合物和醋酸鈷四水合物水溶液中先溶入〇 222克平均分子量為ι〇,〇〇〇 Γ 之聚乙烯吡咯酮’稱取硼氫化納〇 227克(6毫莫耳^默克公司广將其以3 毫升去離子水與3毫升99.9 %曱醇溶解；在氮氣下，在25t將醋酸鎳水溶 •液放於錐形瓶内，以磁石攪拌混合之，再以蠕動泵浦緩慢滴入硼氫化鈉水 /谷液即生成黑色觸媒，將觸媒以去離子水洗滌3次後，再以99·9 %曱醇 洗務2次。 實施例3 : Q ^ " 製備PVP/Ni莫耳數比為5之高分子穩定化鎳與鈷觸PVP-NiCoB(5)， 莫耳數算法以一個PVP單體為單位，製備方法同比較例丨，於〇1 M醋酸 鎳四水合物和醋酸鈷四水合物水溶液中先溶入m克平均分子量為1〇,〇〇〇 之聚乙烯吡咯酮，稱取硼氫化鈉0.227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 %曱醇溶解；在氮氣下，在25。(：將醋酸錄水溶 液放於錐形瓶内，以磁石攪拌混合之，再以蠕動泵浦缓慢滴入硼氫化鈉水 /谷液’即生成黑色觸媒；將觸媒以去離子水洗滌3次後，再以999 %曱醇 15 200902147 洗蘇2次。 實施例4 : 製備PVP/Ni莫耳數比為10之高分子穩定化鎳與録觸 PW-NiC〇B(10)，莫耳數算法以一個PVP單體為單位，備方法同比較例}, 於0_1 Μ醋酸鎳四水合物和醋酸鈷四水合物水溶液中先溶入2 克平均八 子量為ιο,οοο之聚乙烯吡咯酮，稱取硼氫化鈉0·227克(6毫莫耳）（默克八 Π 司），將其以3毫升麵子水與3毫升99.9 %曱醇溶解；在氮氣下，在25 。(：將醋酸鎳水溶液放於錐形瓶内’以磁石授拌混合之，再以罐動栗浦緩慢 滴入删氫化鈉水溶液，即生成黑色觸媒；將觸媒以去離子水洗務3次後， 再以99.9 %甲醇洗滌2次。 實施例5 : 製備PVP/Ni莫耳數比為2〇之高分子穩定化鎳與姑觸 〇 PVP_NiCGB(2G)，料數算如—個pvp單體絲位，製備方法同比較例1， 於0.1 Μ醋酸錦四水合物和醋酸姑四水合物水溶液巾先溶人4.44克平均分 子量為聊0之聚乙烯对酮，稱_氫化納〇 227 _毫莫耳）（默克公 司）’將其以3 $升去離子水與3毫升99 9 %曱醇溶解；在氮氣下，在25 °C將醋_水溶液放於錐形瓶内，以磁石·混合之，再以螺動泵浦缓慢 滴入石朋II化鈉水溶液’即生成黑色觸媒；將觸媒以去離子水洗務3次後， 再以99.9 %甲醇洗滌2次。 比較例2 : 16 200902147 將比較例！製備之觸媒與2_54克的對氯硝基苯、8〇毫升曱醇皆置於反 應益内，先以氫氣沖洗反應系統10分鐘，以除去系統内的空氣；先以低速 授拌(約卿印叫，並升溫至反應溫度则。c，同時逐步加壓至反應壓力16〇 P蚱’待溫度與壓力到達反應條件時，增加攪拌速度至500啊，此時定為 反應開始_ (t=G);每1G分鐘中間取樣_次，取獅先溢流約1G滴之樣 液，以排除取樣管中前批樣液殘留所造成之誤差；反應完畢後，停止氣氣 供給’並依次降溫、降壓，將樣品以氣相色層分析儀(中國層析WOO 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英吋之不繡鋼管， 填充物為 5% OV-1 〇 1/80-100 mesh Chromosorb WAW-DMSC。 . 實施例6 : 同比較例2 反應結果如下： 時間（分鐘） 10 20 30 40 對氯硝基苯轉化 率（％) 29.07 38.68 92.35 100 對氣苯胺選擇率 99.9% 99.9% 99.9% 99.9% 實施例7 : 同比較例2，惟改用實施例1之PVP-NiCoB(0_25)觸媒。 反應結果如下： 時間（分鐘） 10 20 30 40 50 60 對氯瑞基苯轉化率 (%) 20.42 38.68 74.95 93.32 94.50 100 對氣苯胺選擇率 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 實施例8 : 同比較例2，惟改用實施例2之PVP- NiCoB (1)觸媒。 17 200902147 反應結果如下： 時間（分鐘） 10 20 30 40 50 60 70 80 對氯硝基苯轉化率 (%) 1.48 2.56 6.16 14.04 52.08 87.72 98.14 100 對氯苯胺選擇率 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 實施例9 : 同比較例2，惟改用實施例3之PVP- NiCoB (5)觸媒。 反應結果如下： 時間（分鐘） 10 20 30 40 50 對氣硝基苯轉化率 (%) 1.58 2.36 14.27 45.21 85.34 對氣苯胺選擇率 99.9% 99.9% 99.9% 99.9% 99.9% 時間（分鐘） 60 70 80 90 100 對氣硝基苯轉化率 (%) 92.17 95.58 97.86 99.12 100 對氣苯胺選擇率 99.9% 99.9% 99.9% 99.9% 99.9% 實施例10 : 同比較例2，惟改用實施例4之PVP- NiCoB (10)觸媒。 反應結果如下： 時間（分鐘） 10 20 30 40 50 對氣硝基苯轉化率 (%) 2.011 14.89 49.11 67.07 84.01 對氣苯胺選擇率 99.9% 99.9% 99.9% 99.9% 99.9% 時間（分鐘） 60 70 80 90 100 對氣硝基苯轉化率 (%) 87.28 92.55 95.37 97.54 100 18 200902147 對氣苯 "—99.9% 99.9% 99.9% 99.9%~~~~99^9% 實施例11 : 同比較例2，惟改用實施例4之PVP-NiCoB (20)觸媒 反應結果如下： 時間（分鐘） 10 20 30 40 50 60 ----— 對氯硝基苯轉 化率（％) 0.11 0.12 0.42 0.73 1.05 1.33 ----— 對氣苯胺選擇 0% 0% 0% 0% 0% 0% _^--^ 時間（分鐘） — 70 80 90 100 110 _--- 120 _____- 對氣硝'基苯轉 化率（％) 1.35 1.57 1.93 2.01 2.591 8.98 ______— 對氯苯胺選 率 0% 0% 0% 0% 0% 0.07%The aniline; the hydrogen pressure for the hydrogenation reaction is preferably from 5 to 15 atm; and the hydrogenation reaction is preferably carried out at a temperature of from 50 to 10 °C. • The polymer-stabilized NiCoB alloy catalyst produced by the present invention is characterized by a black nano-solid particle having a particle size of between 3-5 nm and a second characteristic for liquid phase hydrogenation of a halogen-based aromatic group. It has high catalytic activity and can rapidly hydrogenate p-chloroschhylbenzene to p-aniline. Polymer-stabilized nickel and cobalt alloy catalysts are mainly used in the reaction of gas-nitrogen hydrogenation to p-aniline aniline. The main equipment is stainless steel electromagnetic stirring high-pressure reactor. It adopts semi-batch operation, and the total j pressure in the reactor is hydrogen cylinder. The pressure regulating valve of the outlet is controlled and maintained at a constant pressure. The step is to first flush the prepared fresh PVP-Ni C〇xBy catalyst into the reactor with the reaction solvent and add the reactants at 30-60 ml under atmospheric pressure. Min hydrogen rushed for 10-20 minutes to drive off the air in the reactor, and slowly heated to a reaction temperature of 5〇_1〇〇 at a low speed of ι〇〇_2〇〇rpm. (3, then pressurizing with helium to a reaction pressure of 5 to 15 atm, increasing the stirring rate to 300-700 rpm, and starting the reaction. 13 200902147 [Embodiment] Comparative Example 1 · Preparation of nickel and cobalt catalyst NicoB, said Take ο··74 g (2 mmol) of acetic acid bromine tetrahydrate (Merck λ Division) and 0.0498 gram (〇. 2 mmol) of acetic acid tetrahydrate (Merck) at 25_ flat cone ^ / in the bottle 'add 10ml deionized water and 1GmJ f alcohol (> 99%) Na Rimole concentration of 〇 1 Μ and cobalt molar concentration of α 〇 1 Μ solution, and then weigh Q. Sodium (Merck) (deleted with a nickel molar ratio of 3) in a beaker 'Add 3 river deionized water and 3 ml of methanol to a molar concentration of 1 ,, Valley liquid 'conical flask in the electromagnetic win The magnet is passed under the mixing of the magnet and the nitrogen is removed to exclude the second gas. The new micro-wei green is used to transfer the sodium water into the nickel salt aqueous solution at a rate of 2 ml/min. The dripping process will quickly produce black Ni (10). Touching the particles, and generating a large amount of nitrogen emulsions, the side sodium hydride aqueous solution is added and no longer generates hydrogen bubbles, and the reaction is stopped. The NiCoB catalyst is separated from the solvent by a high-speed centrifuge to remove The sub-water column was washed three times, and then washed twice with a decyl alcohol (>99%) solution, and the obtained catalyst was an amorphous structure (XRD analysis), and the particle diameter was 3-5 nm (TEM analysis). Preparation of PVP/Ni molar ratio of 〇_25 polymer stabilized nickel and cobalt touch PVP-NiCoB (0.25) 'Mole number algorithm in a pvp monomer unit, the preparation method is the same as Comparative Example 1 ' at 0.1 Μ Nickel acetate tetrahydrate and acetic acid tetrahydrate aqueous solution first dissolved into ο..% grams of average molecular weight of 10,000 polyvinylpyrrole, said sodium borohydride 0 227 grams (6 millimoles) (Merck ), it was dissolved in 3 ml of deionized water and 3 ml of 99.9% methanol; under nitrogen, the nickel acetate aqueous solution was placed in an Erlenmeyer flask at 14 200902147 25 ° C, and the magnet was mixed, and then Lipu was compiled. The black sodium catalyst was slowly added dropwise to form a black catalyst; the catalyst was washed three times with deionized water, and then washed twice with 99.9% methanol. Example 2: Preparation of PVP/Ni molar ratio is i The polymer stabilization record and the PVP-NiCoB(l), the molar number algorithm is based on a PVP monomer, and the preparation method is the same as the comparison. 〇ι Μ Nickel acetate tetrahydrate and cobalt acetate tetrahydrate aqueous solution first dissolved in 〇 222 grams of average molecular weight ι〇, 〇〇〇Γ of polyvinylpyrrolidone 'weighed 227 grams of sodium borohydride (6 millimoles Ears ^ Merck Company widely dissolved it with 3 ml of deionized water and 3 ml of 99.9% sterol; under nitrogen, put nickel acetate water soluble solution in a conical flask at 25t, stir and mix with magnet, then The peristaltic pump was slowly dropped into the sodium borohydride water/guar solution to form a black catalyst. After the catalyst was washed three times with deionized water, it was washed twice with 99.9% sterol. Example 3: Q ^ " Preparation of PVP/Ni molar ratio of 5 polymer stabilized nickel and cobalt touch PVP-NiCoB (5), Moll number algorithm in a PVP monomer unit, the preparation method is the same For example, in the aqueous solution of 1 M nickel acetate tetrahydrate and cobalt acetate tetrahydrate, m g of an average molecular weight of 1 〇, polyvinylpyrrolidone of hydrazine, and 0.227 g of sodium borohydride (6 m) are first dissolved. Mohr) (Merck), dissolved in 3 ml of deionized water with 3 ml of 99.9% sterol; under nitrogen, at 25. (: The aqueous solution of acetic acid is placed in an Erlenmeyer flask, stirred and mixed with a magnet, and then slowly dropped into the sodium borohydride water/trol solution by a peristaltic pump to generate a black catalyst; the catalyst is washed with deionized water 3 After that, the sodium was washed twice with 999% decyl alcohol 15 200902147. Example 4: Preparation of a polymer-stabilized nickel with a PVP/Ni molar ratio of 10 and a touch of PW-NiC〇B (10), Mohr The number algorithm is in the form of a PVP monomer, and the preparation method is the same as in the comparative example}. In the 0_1 Μ nickel acetate tetrahydrate and the cobalt acetate tetrahydrate aqueous solution, 2 g of the average octagonal amount of peopone of ιο, οοο is firstly dissolved. Weigh 0. 227 g (6 mmol) of sodium borohydride (Merke Bacillus), dissolve it with 3 ml of face water and 3 ml of 99.9% sterol; under nitrogen, at 25 (: will The nickel acetate aqueous solution is placed in a conical flask, and the mixture is mixed with a magnet, and then the sodium sulphate is slowly dropped into the sodium hydride solution to form a black catalyst. After the catalyst is washed with deionized water for 3 times, Washed twice with 99.9% methanol. Example 5: Preparation of polymer-stabilized nickel with PVP/Ni molar ratio of 2〇 and PVP_NiCGB (2G) ), the number of materials is calculated as a pvp monomer filament, the preparation method is the same as that of the comparative example 1, in the 0.1 Μ acetic acid bromine tetrahydrate and the acetic acid tetrahydrate aqueous solution, the first solution is 4.44 g of polyethylene having an average molecular weight of 0 For ketones, weighed _ hydride 〇 227 _ millimoles (Merck) 'dissolve it with 3 $ liters of deionized water and 3 ml of 99 9 % sterol; under nitrogen, vinegar at 25 ° C _ The aqueous solution is placed in a conical flask, and the magnet is mixed with the magnet, and then slowly pumped into the Sipeng II sodium solution by a screw pump to generate a black catalyst; after the catalyst is washed with deionized water for 3 times, 99.9 % methanol was washed twice. Comparative Example 2: 16 200902147 Comparative Example! The prepared catalyst was placed in the reaction with 2 to 54 g of p-chloronitrobenzene and 8 ml of sterol, and the reaction system was first rinsed with hydrogen. Minutes to remove the air in the system; first mix at a low speed (about qing, and raise the temperature to the reaction temperature. c, while gradually pressurizing to the reaction pressure 16 〇 P 蚱 'when the temperature and pressure reach the reaction conditions, Increase the stirring speed to 500 ah, this is the start of the reaction _ (t = G); sampling every 1G minutes _ times, take First overflow the sample of about 1G drop to eliminate the error caused by the residual sample in the sample tube; after the reaction is completed, stop the gas supply 'and sequentially lower the temperature, reduce the pressure, and use the sample as a gas chromatography layer analyzer. (China Chromatography WOO F) Analysis of the concentration of the reactants and products 'The chromatographic column is 3 meters long and the diameter is 1/8 inch of non-embroidered steel pipe. The filling is 5% OV-1 〇1/80- 100 mesh Chromosorb WAW-DMSC. Example 6 : Same as Comparative Example 2 The reaction results were as follows: Time (minutes) 10 20 30 40 Conversion of p-chloronitrobenzene (%) 29.07 38.68 92.35 100 Selectivity of p-aniline was 99.9% 99.9 % 99.9% 99.9% Example 7: Same as Comparative Example 2 except that the PVP-NiCoB (0-25) catalyst of Example 1 was used instead. The reaction results are as follows: Time (minutes) 10 20 30 40 50 60 Conversion of p-chlororeylbenzene (%) 20.42 38.68 74.95 93.32 94.50 100 p-aniline selectivity 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% Example 8 : In the same manner as in Comparative Example 2, the PVP-NiCoB (1) catalyst of Example 2 was used instead. 17 200902147 The reaction results are as follows: Time (minutes) 10 20 30 40 50 60 70 80 Conversion of p-chloronitrobenzene (%) 1.48 2.56 6.16 14.04 52.08 87.72 98.14 100 p-chloroaniline selectivity 99.9% 99.9% 99.9% 99.9% 99.9 % 99.9% 99.9% 99.9% Example 9: Same as Comparative Example 2 except that the PVP-NiCoB (5) catalyst of Example 3 was used instead. The reaction results are as follows: Time (minutes) 10 20 30 40 50 Conversion of p-nitrobenzene (%) 1.58 2.36 14.27 45.21 85.34 Gas aniline selectivity 99.9% 99.9% 99.9% 99.9% 99.9% Time (minutes) 60 70 80 90 100 conversion of p-nitrobenzene (%) 92.17 95.58 97.86 99.12 100 p-aniline selectivity 99.9% 99.9% 99.9% 99.9% 99.9% Example 10: Same as Comparative Example 2, except that PVP of Example 4 was used instead. NiCoB (10) catalyst. The reaction results are as follows: Time (minutes) 10 20 30 40 50 Conversion of p-nitrobenzene (%) 2.011 14.89 49.11 67.07 84.01 Gas aniline selectivity 99.9% 99.9% 99.9% 99.9% 99.9% Time (minutes) 60 70 80 Conversion ratio of 90 100 to nitrobenzene (%) 87.28 92.55 95.37 97.54 100 18 200902147 Benzene "-99.9% 99.9% 99.9% 99.9%~~~~99^9% Example 11: Same as Comparative Example 2, However, the results of the PVP-NiCoB (20) catalyst reaction of Example 4 were as follows: Time (minutes) 10 20 30 40 50 60 ----- Conversion of p-chloronitrobenzene (%) 0.11 0.12 0.42 0.73 1.05 1.33 ----—Select 0% 0% 0% 0% 0% 0% _^--^ Time (minutes) — 70 80 90 100 110 _--- 120 _____- Conversion to gas nitrobenzene Rate (%) 1.35 1.57 1.93 2.01 2.591 8.98 ______—P-chloroaniline selectivity 0% 0% 0% 0% 0% 0.07%
對氯硝基苯液相氫化成對氯苯胺反應 例子 觸媒 反應時間(min) 選擇率(％) 轉化率c 比較例2 NiCoB 20 95.06 73.75 實施例5 PVP-NiCoB(lO) 30 93.51 74.95 實施例6 PVP-NiCoB(20) 60 97.58 87.72 實施例7 PVP-NiCoB(30) 100 99.86 100 實施例8 PVP-NiCoB(40) 90 99.57 97.54 〇 十、申請專利範圍： !· 一種製造高分子穩定化鎳钻棚觸媒的方法，此含高分子穩定化鎳與姑的 觸媒係以鎳的鹽類、鈷的鹽類與高分子聚乙烯吡咯酮溶於溶劑中，再以 19Reaction of liquid phase hydrogenation of p-chloronitrobenzene to p-chloroaniline. Reaction time (min) Selectivity (%) Conversion rate c Comparative Example 2 NiCoB 20 95.06 73.75 Example 5 PVP-NiCoB(lO) 30 93.51 74.95 Example 6 PVP-NiCoB(20) 60 97.58 87.72 Example 7 PVP-NiCoB(30) 100 99.86 100 Example 8 PVP-NiCoB(40) 90 99.57 97.54 〇10, patent application scope: !· A manufacturing of polymer stabilized nickel The method for drilling the catalyst in the shed, the polymer-stabilized nickel and the cation catalyst are dissolved in a solvent by a salt of nickel, a salt of cobalt and a polymer polyvinylpyrrolidone, and then 19