1342233 坎、發明說明： 【發明所屬之技術領域】 τ米科技研發潛力無n，被視為廿—世紀科技與產業發展的最大 轉力。今日的科學小自原子、大至物體的性f，我們都可以清楚的 瞭解。但對於中間的大小(mes㈣aIe)群集(cluster)，其大小約在奈米 區域’現在則仍在探錄段；中間群集雜f異於軒賴，也與一 般物質不大姻，在奈米尺度下，物f會呈現過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性而形成特殊功 月匕其中最有名的就是「荷葉效應」，出於泥而不染、水珠就在有自 然的奈米級絨毛韻表轉成，污泥、雜子不易沾附。 奈米科技就是將原子或分子組合成新的奈米結構，其約介於分子 與次微米結構之間，當元件請料絲本構造縮小到㈣程度，除了 本身變的更小外’其量子效應也不容忽視，許多物性均會改變，如質 量變輕、體積縮小、表面積增加，更重要的是熱導度(鋼的一百倍） 與導電性(銅的-百萬倍)增加，連磁性也跟著改變，而且還具備高表 面積/體積比、高密度堆積的潛力以及高結構組合彈性等特性，應用 祀圍十分廣泛。還可透過對物f極微細尺寸的操縱直接移動原子； 若可隨意操縱組成物質的原子，就能任意改變、創造物質，如：正常 特性_料碎’但奈米級_卻可料，甚至再進—步的研發下， 1342233 未來的電腦可以捲起來帶走都是可能的事；金是惰性金屬，不容易變 化，奈米金卻是防毒面具中極佳的活性劑。 奈米物質隨不同領域有不同的定義，賴媒而言，當觸媒的粒徑 逐漸減小時，其催化性質亦隨之改變。_般而言，粒徑介於M〇〇奈 米之間時’其催化性質能觀顆粒有顯著的差異，即稱為奈米觸媒； 其η在較早之刖觸媒已經是奈米的等級，只是以超微細觸媒稱之。隨 著奈米材料的研究日益辆，錢奈__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-觸媒均為多孔性物質，故有人將孔洞直徑達 奈米級’尤其是指小於1G絲的稱為奈米麟，例如沸石的孔洞直 徑均為奈米級’故亦有人稱其為奈綺料；依孔洞管鮮度定義，也 有人將觸飢壁厚度在奈級的稱為奈_媒，亦稱為奈米結構觸 媒。 奈米粒子具有不同幾何形狀，而奈米結構組成包括結晶、非結 晶、組織、界面層等結構。在催化性質方面，由於奈米粒子體積非常 小’材料表面軒錢斷_子_數_值贿十分顯著，而固 體表面原子的熱穩定性與化學穩紐均較内部原子差得多，因此表面 原子的多寡代表了催化的活性，即絲面積是—個好觸媒材料的基本 要素’如Fe/Zr〇2奈米觸媒可提升C0+H2反應成煙類的催化能力。 1342233 金屬觸媒的活性及選擇性往往與觸媒粒徑、形狀等結構特性， 以及反應齡、碰等環境„息息相關。近年來，奈餘子因其極 微小的粒徑與極大的比表面積，產生避異於塊狀金屬與單一原子之 電、磁、光、熱及化學性質，已在化學、物理、材料科學、生化等相 關領域產出不同的應麟力，諸如催化、電子、磁性記錄婦、高性 能工程材料、染料、接著劑、藥物釋放料，奈米金屬微粒更因極高 的表面原子數’表祕料飽和致表祕性增加，表面_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’使其倍受學解及產料_，已顯絲21世紀催化反應的 主角之一，疋奈米材料研究中不可缺少的重要項目。 超細非晶形(amorphous)合金粒子由於其本身本質上許多特殊的 特性，因而引起多方的注意，例如：短程無序(sh〇rt_range〇㈣、長 辛王有序(l〇ng_rangedlsorder)和高分散性，以及它們在粉末冶金學、磁 性物質、觸媒的應麟力，且這個結合了非晶形及超細合金的粒子、 粉末，具有1.高表面不飽和活性位置2沒有結晶缺陷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 及向穩定性。 本研究所用的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'合成氣曱烷化及水蒸氣重組等等。不過傳統 1342233 的鎳觸媒科因域體孔_燒結、不純物堵塞制或反應物殘留在 ’舌性基上而造成活性衰退。 本發明係有關含氣硝基苯在含有錄與钻的觸媒存在下，與氮氣反 應生成對«胺之製程，此含有鎳触_縣以_魏加入姑之 鹽類，並·氫化物作為還原劑製備而成，其組成可以用Nic〇A表 示，\為〇)與鎳之莫耳比，y為硼與鎳之莫耳比，乂之範圍為〇〇1 $ X S l’y之範圍為〇.〇1 $ y $卜此Nic〇xBy為奈米級顆粒直徑， 其顆粒直徑皆在200奈米以下，且其為非結晶型態，比表面積大於5 m/g，氫化反應係在一於渡反應器進行，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4〇 _ 150 °C之間。此觸媒 對於含氣硝基苯的氫化反應，具有高活性與高產物選擇性的特質，其 產物有99 %以上均是含氯苯胺。 【先前技術】 含氣硝基苯以液態氫化反應生成含氣笨胺的方法，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，用為對氣硝基苯氢 化成對氣苯胺’間氣琐基笨氣化成間氣苯胺，Coq以麵跟釕等貴金 屬，探討觸媒晶粒粒徑大小對於對-氣硝基苯的選擇性氫化的影響[j.1342233 Kan, invention description: [Technical field to which the invention belongs] The potential of research and development of τ米科技 is not n, and it is regarded as the biggest turning point in the development of technology and industry. Today's science is small, from the atom to the nature of the object f, we can clearly understand. But for the middle size (mes (four) aIe) cluster, its size is about the nanometer area 'now it is still in the exploration section; the middle cluster is different from Xuan Lai, and it is not married to the general material, at the nanometer scale. Underneath, the material f will exhibit physicochemical and biological properties that are different from the giant scale. The material will form a special function due to the generation of completely different characteristics. The most famous one is the "Lotus Effect", which is not stained by mud. The water drops are converted into natural nano-grade velvet rhymes, and the sludge and miscellaneous are not easy to adhere. Nanotechnology is the combination of atoms or molecules into a new nanostructure, which is between the molecular and sub-micron structures. When the component is reduced to a (four) degree, the quantum is smaller than itself. The effect can not be ignored, and many physical properties will change, such as lighter weight, smaller volume, increased surface area, and more importantly, thermal conductivity (one hundred times of steel) and conductivity (copper-million times) increase. Magnetics have also changed, and they also have high surface area/volume ratio, high-density stacking potential, and high structural combination elasticity. It is also possible to directly move atoms through the manipulation of the extremely fine size of the object f; if the atoms constituting the substance can be manipulated at will, the material can be arbitrarily changed and created, such as: normal characteristics _ smashed 'but the nano-grade _ can be expected, even In the further development of the step-by-step, 1342233, it is possible that the future computer can be rolled up and taken away; gold is an inert metal and is not easy to change. Nano gold is an excellent active agent in gas masks. Nanomaterials have different definitions in different fields. In terms of media, when the particle size of the catalyst is gradually reduced, the catalytic properties also change. _ In general, when the particle size is between M 〇〇 nanometers, there is a significant difference in the catalytic properties of the particles, which is called nanocatalyst; its η is already nano in the earlier 刖 catalyst. The grade is only called by ultra-fine catalyst. With the increasing research on nanomaterials, the definition of Chennai __ is also chaotic, but there are mainly the following. According to the particle diameter definition - the particle diameter is less than (10) nanometer called nanocatalyst; according to the hole diameter definition - the catalyst is porous, so some people will have a hole diameter of nanometer', especially the less than 1G wire. For the nano-lin, for example, the pore diameter of the zeolite is nanometer', so some people call it a naphtha; according to the definition of the purity of the hole tube, some people will call the thickness of the wall at the nai level. It is called nanostructure catalyst. Nanoparticles have different geometries, while nanostructures include structures such as crystals, non-crystals, structures, interfacial layers, and the like. In terms of catalytic properties, because the nanoparticle volume is very small, the surface of the material is very significant, while the thermal stability and chemical stability of the solid surface atoms are much worse than the internal atoms, so the surface The amount of atoms represents the catalytic activity, that is, the silk area is an essential element of a good catalyst material, such as Fe/Zr〇2 nanocatalyst, which can enhance the catalytic ability of C0+H2 to form a smoke. 1342233 The activity and selectivity of metal catalysts are often related to the structural characteristics such as particle size and shape of the catalyst, as well as the age of reaction, collision, etc. In recent years, Naizi has been extremely small in particle size and extremely large specific surface area. Producing electrical, magnetic, optical, thermal and chemical properties that are avoided from bulk metals and single atoms, and have produced different tactics in the fields of chemistry, physics, materials science, biochemistry, etc., such as catalytic, electronic, and magnetic recording. Women, high-performance engineering materials, dyes, adhesives, drug release materials, nano metal particles are also due to the extremely high surface atomic number, the surface secretivity increases, the surface degree increases with the particle size. The formation of uneven atomic steps increases the contact surface of the chemical reaction, making it a subject of learning and production. It has become one of the main protagonists of the 21st century catalytic reaction, an indispensable important item in the research of nanomaterials. Ultra-fine amorphous alloy particles have attracted many attentions due to their inherently many special characteristics, such as short-range disorder (sh〇rt_range〇(4), Changxinwang has Order (l〇ng_rangedlsorder) and high dispersion, and their role in powder metallurgy, magnetic materials, catalysts, and this combination of amorphous and ultra-fine alloy particles, powder, with 1. high surface desaturation The active site 2 has no crystallographic defect isotropic structure, which makes it highly active, high selectivity and stability to specific reactions. The nickel catalyst used in this study has been widely used in the petrochemical industry. Such as hydrogenation of unsaturated organics, hydrocracking 'syngas alkylation and steam recombination, etc.. However, the traditional nickel-catalyst family of 1342233 is caused by domain pores_sintering, impure blockage or reactant residues in the tongue. The invention relates to the degradation of activity on the base. The invention relates to the reaction of gas-containing nitrobenzene in the presence of a catalyst containing a recording and drilling, and reacting with nitrogen to form a process for the amine, which contains a nickel contact _ county to add wei to the salt The hydride is prepared as a reducing agent, and its composition can be expressed by Nic〇A, which is the molar ratio of nickel to nickel, and y is the molar ratio of boron to nickel. The range of $ XS l'y is 〇. 1 $ y $b This Nic〇xBy is a nanometer particle diameter, the particle diameter is below 200 nm, and it is amorphous, the specific surface area is more than 5 m / g, and the hydrogenation reaction is in a reaction The solvent is an alcohol of four carbons or less, the hydrogen pressure is between 5 and 40 atmospheres, and the reaction temperature is between 4 〇 and 150 ° C. The catalyst has a high hydrogenation reaction of the gas-containing nitrobenzene. The activity and high product selectivity characteristics, more than 99% of the products are chloroaniline. [Prior Art] The method of liquid hydrogenation of gas-containing nitrobenzene to form gas-containing stupid amines, the prior art is based on precious metals Catalyst, which includes three catalysts of palladium, platinum and rhodium, which are used to hydrogenate p-nitrobenzene to p-aniline aniline, which is a gas-to-gas aniline, and Coq is a noble metal such as helium iridium. Effect of particle size on the selective hydrogenation of p-nitrobenzene [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 為對氣硝基苯之氢化反應觸媒；Liao等人之論文[J. Chem. Soc·，Chem. Co_.，第1155-1156頁，1995年]揭示以鈀-釕雙金屬做為對氣硝基苯 1342233 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； 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°比 咯硐）在鉑金屬上’做為對氣硝基苯之氢化反應觸媒。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4，140,719號揭示以相轉移觸媒做為氟化2,4,5-三氣硝基笨 生成2,4-二氟笨胺之方法。以貴重金屬如鉑、鈀或铑金屬做為觸媒， 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，陸續有許多專家' 學者投入硼化金屬觸媒的研究行列，Xie[AppliedCatalysisA,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. ^)c·，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觸媒具有特殊的氫化活性、選擇性及财毒 特性。删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觸媒中對葡萄糖之〇〇鍵氫化有 顯著的促劑效果[Chemistry Letter，第28卷，第629頁，1999年]， Yu[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Co含量添加到Ni-B非晶形合金觸媒中可以増 加氫化反應的活性。Lee [Industrial and Engineering Chemistry Research 1342233 ㈣卷，第剛獨頁，麵锁示不_製備環境對觸媒的表面 型怨、顆粒大似及表面積都雜大的影響，而表面積的大小則是影Molecular Catalysis, Vol. 79, p. 243, 1993]. , Figueras et al. [Applied Catalysis, Vol. 76, pp. 255-266, 1991] reveals the use of base metals as hydrogenation catalysts for p-nitrobenzene; Liao et al. [J. Chem. Soc., Chem. Co., pp. 1155-1156, 1995] discloses the use of a palladium-ruthenium bimetallic as a hydrogenation catalyst for p-nitrophenyl 1342233; a paper by Vitulli et al. [catalysis Letter, Vol. 44 , pp. 205-210, 1997] Reveals the catalytic reaction of platinum/alumina as a hydrogenation reaction for nitrobenzene; Lin et al. [J. Molecular Catalysis A: Chemical, Vol. 159, pp. 115-120 Page, 2000] reveals the addition of the surfactant polyvinyl alcohol (polyethylene pyrrole) on platinum metal as a hydrogenation catalyst for p-nitrobenzene. U.S. Patent No. 4,326,078, the disclosure of which is incorporated herein by reference to U.S. Pat. No. 4,140,719, the disclosure of which is incorporated herein by reference. Stupid method for producing 2,4-difluoro-p-amine. The use of precious metals such as platinum, palladium or rhodium as a catalyst is not only expensive, but also has a high by-product due to its high hydrogenation capacity. 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 his sons before and after the Second World War, there have been many experts who have invested 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 to other Ni-based catalysts such as commercial catalyst Raney Ni. ), Ni-B/Si02 catalysts have shown higher activity and better selectivity for primary amines. Okamoto published a paper in 1979 [j Chem. ^)c., vol. 75, p. 2027 In 1979, the surface atomic state of P-lNiB catalyst was analyzed by XPS, and the NiB catalyst was explained to have special hydrogenation activity, selectivity and toxic properties. The depleted metal catalyst can also be modified by adding a trace promoter to change the catalytic activity or selectivity. Deng et al found that the addition of tungsten (W) has a significant promoter effect on the hydrogenation of glucose in the CoB catalyst [Chemistry Letter, Vol. 28, p. 629, 1999], Yu [Applied Catalysis A:, Vol. 163, pp. 1-13, 1997] Reduction of a solution containing a nickel salt and a cobalt salt with potassium borohydride by chemical reduction. The Ni-Co-B bimetallic alloy catalyst was prepared. The results showed that the addition of a moderate Co content to the Ni-B amorphous alloy catalyst can be used for the hydrogenation reaction. Lee [Industrial and Engineering Chemistry Research 1342233 (4) volume, the first single page, the surface lock shows no _ preparation environment on the surface of the catalyst type complaints, particle size and surface area are mixed, and the surface area is the shadow
Liu [Industrial and Engineering Chemistry Research，第45卷，第62-69頁，2_年]揭示在2挪及充滿氣氣的環 境下製備NiPB麟’可以得珊含氣£肖絲的統反應有最好活性 的NiPB舰，並且綱反鱗介麟反應哺化率雜大的影響， 使用曱醇會比使用乙醇獲得更高的轉化率。含氣硝絲的氫化反^可 以用下列反應式表示，其副產物非常多，—般以含氣苯胺為所希望產 生的物質。Liu [Industrial and Engineering Chemistry Research, Vol. 45, pp. 62-69, 2_Y] reveals that NiPB Lin can be prepared in a 2 atmosphere and full of gas. The activity of NiPB is very active, and the effect of hybridization of the cytoplasmic cytoplasmic reaction is higher. The use of sterols will result in higher conversion than ethanol. The hydrogenation reaction of the gas-containing nitrocellulose can be represented by the following reaction formula, and there are many by-products, and the gas-containing aniline is generally desired.
經電腦檢索美國專利有關p-CNB氫化反應製程，有下列與本案有 關之專利： 專利編號 專利名稱 1 7,091,383 Method for the production of amines 1342233 2 7,064,237 Method for the production of amines 3 6,894,193 Method for hydrogenating liquid organic compounds 4 6,815,562 Process for the preparation of nitrodiphenylamines 5 6,469,181 Process for preparing 2-oxindoles and N-hydroxy-2-oxindoles 6 6,350,911 Method for producing amines 7 6,316,381 Multimetallic catalyst and process for preparing substituted aromatic amines 8 6,197,716 Process for the production of aromatic halogen-amino compounds 9 5,977,411 Catalytic hydrogeneration of nitrobenzene to 4-aminodiphenylamine in the presence of a hydroxyl compound and a solvent 10 5,962,741 Process for the production of aromatic halogen-amino compounds 11 5,545,754 Process for the preparation of p-amino-phenols 12 5,304,680 Process for the preparation of aromatic amines which are substituted by C.sub.l -C.sub.4 -alkoxy in the p-position 13 5,302,742 Process for the preparation of N-acylated p-amino-phenols 14 5,126,485 Process for the hydrogenation of halogenonitro-aromatic compounds in the presence of a sulfur-containing compound 15 5,068,436 Hydrogenation of halonitrobenzenes without dehalogenation 16 4,625,062 Process for producing 4-alkoxyanilines 17 4,551,551 Preparation of bis(aminophenyl) ethers from (N-acetyl)aminophenols or their phenolates 18 4,539,428 Preparation of diaminodiphenyl ethers 19 4,535,162 Process for catalytically reducing nitroaromatic compounds 20 4,375,550 Hydrogenation of halogen-substituted aromatic nitro compounds 21 4,326,081 Conversion of mononitro aromatic compounds to amino compounds by hydrogen sulfide 22 4,326,078 Process for preparation of hydrazobenzenes by catalytic hydrogenation of nitrobenzenes 23 4,287,365 Reduction of aromatic nitro compounds with Raney nickel catalyst 24 4,264,526 Borate reduction of nitrophenols 25 4,230,637 Process for the preparation of chlorine-substituted aromatic amines 26 4,217,307 Process for the preparation of 2,2'-dichIoro-hydrazobenzene 27 4,212,824 Hydrogenation catalyst with improved metallic distribution, its preparation and use for the reduction of aromatic nitro compounds 28 4,185,036 Hydrogenation of mixed aromatic nitrobodies 29 4,140,719 Solid-liquid phase transfer catalysis improved method of preparing 2,4-difluoroaniline 30 4,070,401 Method for the preparation of a halogenated aromatic amine 31 4,059,627 Chlorinated aromatic amines 32 3,989,756 Process for the production of halogenated aromatic nnm^rv amirt^Q 33 3,947,480 Dinitro- and diamino arylene disulfones 34 3,941,717 Process for the production of a catalyst comprising a novel metal on activated carbon 35 3,933,829 4-Aminoquinoline derivatives " 1342233 已公開之專利及文獻中，未有如本發明使用鎳結硼之奈米觸媒作 為含氣硝基笨氩化反應，生成含氣苯胺之觸媒。 【發明内容】 本發明係有關含氣硝基笨在含有鎳與鈷的觸媒存在下與氩氣反 應生成對氣本私之製程’此含有錄與钻的觸媒係以錄的鹽類加入含有 結之鹽類，並以爛氫化物作為還原劑製備而成，其組成可以用Nic〇xBy 表示，X為Co與鎳之莫耳比，y為硼與鎳之莫耳比，乂之範圍為〇 S X S l，y之範圍為0. 01 s y $ 1’此NiC〇xBy為奈米級顆粒直 從’其顆粒直徑皆在1〇0奈米以下’且其為非結晶型態，比表面積大 於5mVg，氫化反應係在-雜反應器進行，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4〇至15〇之 間。此觸制於含氣硝絲賴化反應，具有高活性與高產物選擇性 的特質’其產物有99 %以上均是含氣苯胺。本發明所揭示之方法製 備含有錄與㈣觸媒，其顆粒直徑在奈米範圍，表_大，而且錄係 从非結晶㈣存在’此觸雜於含氣硝絲的氫化反應，具有高活性 1342233 與高產物選擇性的特質，亦即其產物有99 %以上均是含氣苯胺。其 丁硼虱化物係硼氫化鈉或蝴氫化鉀；氫化反應之溶劑以甲醇或乙醇為 最佳；製備觸媒時以在20至7〇r之溫度為最佳；製備觸媒時以在不 含氧之氣氛下製備，例如氮氣或氫氣下，滴入硼氫化物為最佳；含氮 硝基笨為間氣硝基苯或對氣硝基笨，其產物為間氣笨胺或對氣苯胺； 氢化反應之氩氣壓力最佳是在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。 【實施方式】 實施方式1 : 稱取醋酸鎳0.4731克(2毫莫耳X默克公司），將其以1〇毫升去離 子水與10毫升99.9 %甲醇溶解;稱取硼氫化鈉〇227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 %甲酵溶解；在氮氣 下，在25C將醋酸鎳水溶液放於錐形瓶内，以磁石搜拌混合之，再 以蠕動泵浦緩慢滴入硼氫化鈉水溶液，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。 實施方式2: 稱取醋酸鎳0.4831克(2毫莫耳），醋酸鈷〇 〇〇5〇克（Sh〇wa Chemicals，Japan) ’將其以10毫升去離子水與毫升99.9 %甲醇溶 解；稱取硼氮化鈉0.227克(6毫莫耳），將其以3毫升去離子水與3 1342233 宅升99·9 /曱醇溶解，在I氣下，在25°C將醋酸錄水溶液放於錐形 瓶内，以磁石攪拌混合之，再以蠕動泵浦緩慢滴入硼氫化鈉水溶液， 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 洗滌2次。 實施方式3 : 稱取醋酸鎳0.4831克(2毫莫耳），醋酸鈷〇丨奶4克（sh〇waThe U.S. patents relating to the p-CNB hydrogenation process are searched by computer. The following patents are related to the case: Patent No. Patent Name 1,7,091,383 Method for the production of amines 1342233 2 7,064,237 Method for the production of amines 3 6,894,193 Method for hydrogenating liquid organic compounds 4 6,815,562 Process for the preparation of nitrodiphenylamines 5 6,469,181 Process for preparing 2-oxindoles and N-hydroxy-2-oxindoles 6 6,350,911 Method for producing amines 7 6,316,381 Multimetallic catalyst and process for preparing substituted aromatic amines 8 6,197,716 Process for the production of aromatic amines -amino compounds 9 5,977,411 Catalytic hydrogeneration of nitrobenzene to 4-aminodiphenylamine in the presence of a hydroxyl compound and a solvent 10 5,962,741 Process for the production of aromatic halogen-amino compounds 11 5,545,754 Process for the preparation of p-amino-phenols 12 5,304,680 Process For the preparation of aromatic amines which are substituted by C.sub.l - C.sub.4 -alkoxy in the p-position 13 5,302,742 Process for the preparation of N-acylated p-amino-phenols 14 5,126,485 Process for the hydrogenation of halogenonitro-aromatic compounds in the presence of a sulfur-containing compound 15 5,068,436 Hydrogenation Of halonitrobenzenes without dehalogenation 16 4,625,062 Process for producing 4-alkoxyanilines 17 4,551,551 Preparation of bis(aminophenyl) ethers from (N-acetyl)aminophenols or their phenolates 18 4,539,428 Preparation of diaminodiphenyl ethers 19 4,535,162 Process for catalytically reducing nitroaromatic compounds 20 4,375,550 Hydrogenation of halogen - substituted aromatic nitro compounds 21 4,326,081 Conversion of mononitro aromatic compounds to amino compounds by hydrogen sulfide 22 4,326,078 Process for preparation of hydrazobenzenes by catalytic hydrogenation of nitrobenzenes 23 4,287,365 Reduction of aromatic nitro compounds with Raney nickel catalyst 24 4,264,526 Borate reduction of nitrophenols 25 4,230,637 Pr Ocess for the preparation of chlorine-substituted aromatic amines 26 4,217,307 Process for the preparation of 2,2'-dichIoro-hydrazobenzene 27 4,212,824 Hydrogenation catalyst with improved metallic distribution, its preparation and use for the reduction of aromatic nitro compounds 28 4,185,036 Hydrogenation of mixed Aromatic nitrobodies 29 4,140,719 Solid-liquid phase transfer catalysis improved method of preparing 2,4-difluoroaniline 30 4,070,401 Method for the preparation of a halogenated aromatic amine 31 4,059,756 Chlorinated aromatic amines 32 3,989,756 Process for the production of halogenated aromatic nnm^rv amirt^Q 33 3,947,480 Dinitro- and diamino arylene disulfones 34 3,941,717 Process for the production of a catalyst comprising a novel metal on activated carbon 35 3,933,829 4-Aminoquinoline derivatives " 1342233 In the published patents and documents, there is no use of nickel boron as in the present invention. The nanocatalyst reacts as a gas-containing nitro group to form a gas-containing aniline catalyst. SUMMARY OF THE INVENTION The present invention relates to a process in which a gas-containing nitro group is reacted with argon in the presence of a catalyst containing nickel and cobalt to form a gas-to-gas process, and the catalyst system containing the recorded and drilled is added to the recorded salt. It contains a salt of a knot and is prepared by using a ruin hydride as a reducing agent. The composition can be represented by Nic〇xBy, X is the molar ratio of Co to nickel, and y is the molar ratio of boron to nickel. For 〇SXS l, the range of y is 0. 01 sy $ 1' This NiC〇xBy is a nano-sized particle straight from 'the particle diameter is below 1 〇 0 nm' and it is amorphous, specific surface area More than 5 mVg, the hydrogenation reaction is carried out in a hetero-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 4 and 15 Torr. This is in contact with a gas-nitrocellulose reaction, which has high activity and high product selectivity. More than 99% of the products are gas-containing aniline. The method disclosed in the invention prepares a catalyst containing (4) catalyst, the particle diameter is in the range of nanometer, the table is large, and the recorded system is from the non-crystalline (four) hydrogenation reaction which is mixed with the gas-containing nitrocellulose, and has high activity. 1342233 is characterized by high product selectivity, that is, more than 99% of its products are gas-containing aniline. The butyl boron telluride is sodium borohydride or potassium hydrogen hydride; the solvent for hydrogenation is preferably methanol or ethanol; the catalyst is preferably at a temperature of 20 to 7 Torr; when the catalyst is prepared, In the preparation of an oxygen-containing atmosphere, such as nitrogen or hydrogen, it is preferred to add borohydride; the nitrogen-containing nitro group is a gas nitrobenzene or a gas nitro stupid, and the product is an intermediate gas or a gas. Aniline; the argon pressure of the hydrogenation reaction is preferably 5 to 15 atm; and the reaction temperature of the hydrogenation reaction is preferably between 50 and 10 °C. [Embodiment] Embodiment 1: 0.4731 g of nickel acetate (2 mmol Mox) was weighed and dissolved in 1 mL of deionized water and 10 ml of 99.9% methanol; 227 g of sodium borohydride was weighed. (6 mM) (Merck) 'Dissolve it in 3 ml of deionized water and 3 ml of 99.9% of the yeast; put the nickel acetate solution in a conical flask at 25 C under nitrogen, and mix it with magnets. After mixing, the sodium borohydride aqueous solution was slowly dropped by a peristaltic pump to form a black catalyst; after the catalyst was washed three times with deionized water, it was washed twice with 99.9% sterol. Embodiment 2: 0.4831 g (2 mmol) of nickel acetate and 5 g of cobalt acetate (Sh〇wa Chemicals, Japan) were weighed and dissolved in 10 ml of deionized water and 99.9 % of methanol; Take 0.227 g of boron borohydride (6 mmol), dissolve it with 3 ml of deionized water and 3 1342233 Zeng 99.9 / decyl alcohol, and place the aqueous solution of acetic acid at 25 ° C under I gas. In the conical flask, the magnet was stirred and mixed, and then the sodium borohydride aqueous solution was slowly dropped by peristaltic pumping to form a black catalyst; after the catalyst was washed 3 times with deionized water, it was washed with 99.9 % sterol 2 Times. Embodiment 3: Weigh 0.4831 g (2 mmol) of nickel acetate, 4 g of cobalt acetate milk (sh〇wa
Chemicals，Japan) ’將其以1〇毫升去離子水與1〇毫升99 9 %曱醇溶 解；稱取硼氫化鈉0.227克(6毫莫耳），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25〇c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氳化鈉水溶液， 即生成黑色觸媒，將觸媒以去離子水洗蘇3次後，再以99.9 %曱醇 洗滌2次。 實施方式4: 稱取醋酸錄0.4831克(2毫莫耳），醋酸敍〇 4981克（Sh_ Chemicals，Japan)，將其以10毫升去離子水與1〇毫升99 9 %曱醇溶 解；稱取喊化鈉〇.227克(6毫莫耳），將其以3毫升去離子水與3 毫升99.9 %甲醇溶解；在氬氣下，在乃它將醋酸錄水溶液放於錐形 瓶内，⑽石觀混合之，再以螺絲_慢滴人喊化鈉水溶液， 即生成黑色觸媒’將觸媒以去離子水洗條3 ；：欠後，再以99 9 %甲醇 1342233 洗務2次。 實施方式5 : 稱取醋酸鎳〇.483丨克(2毫莫耳），醋酸钻丨4944克⑽魏Chemicals, Japan) 'Dissolve it in 1 mL of deionized water with 1 mL of 99% decyl alcohol; weigh 0.227 g (6 mmol) of sodium borohydride and add 3 ml of deionized water to 3 ml. 99.9% methanol was dissolved; under nitrogen, the nickel acetate aqueous solution was placed in an Erlenmeyer flask at 25 ° C, stirred and mixed with a magnet, and then slowly dropped into the aqueous solution of sodium borohydride by a peristaltic pump to form a black catalyst. After the catalyst was washed with deionized water for 3 times, it was washed twice with 99.9% sterol. Embodiment 4: 0.4831 g (2 mmol) of acetic acid was weighed, and 4981 g of acetic acid (Sh_Chemicals, Japan) was weighed and dissolved in 10 ml of deionized water and 1 ml of 99 9 % decyl alcohol; Sodium sulphate. 227 g (6 mmol), which was dissolved in 3 ml of deionized water and 3 ml of 99.9% methanol; under argon, it was placed in an Erlenmeyer flask, (10) Stone view mixed, and then use the screw _ slow drop people to smash the sodium solution, that is, the black catalyst is generated. The catalyst is washed with deionized water 3; after owing, it is washed twice with 99 9 % methanol 1342233. Embodiment 5: Weighing nickel acetate 〇.483 gram (2 millimolar), acetic acid drill 丨4944 gram (10) Wei
Chermcals，Ja_，將其以1〇毫升去離子水與ι〇毫升99 9 %甲醇溶 解，稱取蝴氫化鈉〇·227克(6毫莫耳），將其以3毫升去離子水與3 毫升99.9 /〇甲醇’谷解’在氮氣下，在坑將醋酸錄水溶液放於錐形 瓶内’以磁石攪拌混合之’再明練浦緩慢滴人她化納水溶液， 即生成黑色觸媒；將觸媒以去離子水絲3次後，再以 %甲醇 洗滌2次。 實施方式6 : 將實施方式1觸媒、2.54克的對氣硝基笨與8〇毫升曱醇皆置於反應 器内；先以氫氣沖洗反應系統1G分鐘，以除去系統内的空氣；先 以低速搜拌(約100 rpm)，並升溫至反應溫度卿。c，同時逐步加壓 至反應壓力160psig ’待溫度與壓力到達反應條件時，增加授摔速 度至5〇〇rpm，此時定為反應開始_ 〇 = 〇);每1〇分鐘中間取樣 -次’取樣時先溢流A 1G滴之樣液，轉除取樣f中前批樣液殘 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㈣㈣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英忖之不输鋼管，填充 1342233 反應結果如下： 物為 5% 〇V-101/80-100meshChromosorb WAW-DMSC。 時間（分鐘） 10 20 30 40 50 60 70 80 對氣硝基笨 轉化率（％) 0 0 5.58 63.3 84.28 98.73 99.07 100 對氣笨胺選 擇率 99.9% 99.9% 99.9% 99.9% 99.9% 99.9%1 99.9%1 99.9% 實施方式7: 將實施方式2觸媒、2.54克的對氣硝基苯與8〇毫升甲醇皆置於反應 器内；先以氫氣沖洗反應系統1〇分鐘，以除去系統内的空氣；先 以低速攪拌(約lOOrpm)，並升溫至反應溫度1〇〇〇c，同時逐步加壓 至反應壓力160psig，待溫度與壓力到達反應條件時，增加攪拌速 度至500 rpm，此時定為反應開始時刻（1=〇);每1〇分鐘中間取樣 一次，取樣時先溢流約10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英吋之不繡鋼管，填充 物為 5% ΟV-1 〇 1/80-1 〇〇 mesh Chromosorb WAW-DMSC。 反應結果如下：Chermcals, Ja_, dissolved in 1 ml of deionized water and 1 ml of 99% methanol, weighed 227 g (6 mmol) of sodium hydride, and 3 ml of deionized water and 3 ml. 99.9 / 〇 methanol 'gluten' under nitrogen, put the aqueous solution of acetic acid in the pit in the pit 'mixed with the magnet' and then slowly swell the aqueous solution, which will produce a black catalyst; After the catalyst was deionized water wire 3 times, it was washed twice with % methanol. Embodiment 6: Embodiment 1 catalyst, 2.54 g of p-nitrobenzene and 8 ml of sterol are placed in a reactor; the reaction system is first flushed with hydrogen for 1 G minutes to remove air in the system; Mix at low speed (about 100 rpm) and raise the temperature to the reaction temperature. c, at the same time gradually pressurize to the reaction pressure of 160 psig 'When the temperature and pressure reach the reaction conditions, increase the drop speed to 5 rpm, which is determined as the start of the reaction _ 〇 = 〇); sampling every 1 〇 minute - times 'When sampling, first overflow the sample of A 1G, and remove the error caused by the residual of the sample before sampling f; after the reaction is completed, stop the hydrogen supply, and then cool down and reduce the pressure; The analyzer (China Chromatography (4) (4) analyzes the concentration of the reactants and products. The chromatographic column is 3 meters long and the diameter is 1/8 inch. The filling result is as follows: The content is 5% 〇V- 101/80-100meshChromosorb WAW-DMSC. Time (minutes) 10 20 30 40 50 60 70 80 Conversion to gas nitro stupid (%) 0 0 5.58 63.3 84.28 98.73 99.07 100 Selectivity of gas stupid amine 99.9% 99.9% 99.9 % 99.9% 99.9% 99.9%1 99.9%1 99.9% Embodiment 7: Embodiment 2 catalyst, 2.54 g of p-nitrobenzene and 8 ml of methanol are placed in the reactor; the reaction system is first flushed with hydrogen 1 minute to remove air from the system; first stir at low speed (about lOOrpm) And heating to a reaction temperature of 1 〇〇〇 c, while gradually pressurizing to a reaction pressure of 160 psig, when the temperature and pressure reach the reaction conditions, increase the stirring speed to 500 rpm, which is determined as the reaction start time (1 = 〇); Sampling once every 1 minute, first overflowing about 10 drops of sample solution to eliminate the error caused by the residual sample solution in the sampling tube; after the reaction is completed, 'stop the hydrogen supply, and then cool down and reduce the pressure; The sample was analyzed by gas chromatography layer analyzer (China Chromatography 8700 F). The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel pipe, and the filling was 5 % ΟV-1 〇1/80-1 〇〇mesh Chromosorb WAW-DMSC. The reaction results are as follows:
對氣硝基笨轉化（％) 12.7 —^ ^^— | 99.9% | 99,91ΓΓ^Γ|~^Γ~^· 實施方式8 : 1342233 將實施方式3觸媒、2.54克的對氣硝基苯與8〇毫升甲醇皆置於反應 器内；先以氫氣沖洗反應系統10分鐘，以除去系統内的空氣；先 以低速攪拌(約1〇〇 rpm) ’並升溫至反應溫度丨〇〇。(：，同時逐步加壓 至反應壓力160psig，待溫度與壓力到達反應條件時，增加攪拌速 度至500 rpm，此時定為反應開始時刻（t=0);每1〇分鐘中間取樣 一次，取樣時先溢流約10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英吋之不繡鋼管，填充 物為 5% OV-101/80-100 mesh Chromosorb WAW-DMSC 〇 反應結果如下： 時間（分鐘） 10 20 30 40 50 60 70 對氣硝基笨轉化率 (%) 15.5 19.1 52.48 81.72 95.95 99.85 100 對氣笨胺選擇率 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 實施方式9: 將實施方式4觸媒、2.54克的對氣硝基苯與80毫升甲醇皆置於反應 器内；先以氫氣沖洗反應系統10分鐘，以除去系統内的空氣：先 以低速攪拌(約l〇〇rpm)，並升溫至反應溫度10(rc，同時逐步加壓 至反應壓力160 psig，待溫度與壓力到達反應條件時，增加攪拌速 度至500rpm，此時定為反應開始時刻〇 = 〇);每1〇分鐘中間取樣 1342233 一次，取樣時先溢流約ίο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英吋之不繡鋼管，填充 物為 5% OV-101/80-100 mesh Chromosorb WAW-DMSC。 反應結果如下： 時間（分鐘） 10 20 30 40 50 60 70 80 對氣硝基笨 轉化率（％) 11.5 26.5 60 78.21 89.2 96.51 99.66 100 對氣苯胺選 擇率 99.9% 99.9%1 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 實施方式10 : 將實施方式5觸媒、2.54克的對氣硝基苯與8〇毫升甲醇皆置於反應 器内，先以虱氣沖洗反應糸統10分鐘，以除去系統内的空氣；先 以低速攪拌(約lOOrpm)，並升溫至反應溫度1〇〇〇c，同時逐步加壓 至反應壓力160psig，待溫度與壓力到達反應條件時，增加搜拌速 度至500rpm，此時定為反應開始時刻（1=〇);每1〇分鐘中間取樣 -次’取樣時先溢流約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(中國層析議F)分析反應物與產物濃 度，分析之騎管柱為3公尺長，直徑丨/8射之不_管填充 1342233 物為 5% OV-101/80-100meshChromosorb WAW-DMSC。 反應結果如下： 時間（分鐘） 10 20 30 40 50 60 對氣硝基笨 轉化率（％) 0.55 4.7 15.16 40.45 64.93 77.44 對氣笨胺選 擇率 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 時間（分鐘） 70 80 90 100 110 120 對氣硝基笨 轉化率（％) 86.01 89.97 92.56 95.95 97.49 100 對氣苯胺選 擇率 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% 上述實施例結果，繪於第一圖。 第一圖是對氣硝基苯的反應轉化率與反應時間的關係圖。Conversion to gas nitro stupid (%) 12.7 —^ ^^— | 99.9% | 99,91ΓΓ^Γ|~^Γ~^· Embodiment 8 : 1342233 Embodiment 3 catalyst, 2.54 g of p-nitrogen Both benzene and 8 liters of methanol were placed in the reactor; the reaction system was first flushed with hydrogen for 10 minutes to remove air from the system; first stirred at a low speed (about 1 rpm) and warmed to the reaction temperature 丨〇〇. (:, at the same time gradually pressurize to a reaction pressure of 160 psig, when the temperature and pressure reach the reaction conditions, increase the stirring speed to 500 rpm, which is determined as the reaction start time (t = 0); sampling once every 1 minute, sampling When overflowing about 10 drops of the sample solution, the error caused by the residue of the previous batch of sample liquid in the sampling tube is excluded; after the reaction is completed, the hydrogen supply is stopped, and the temperature is lowered and the pressure is lowered in turn; the sample is analyzed by a gas phase chromatography layer. (China Chromatography 8700 F) The concentration of the reactants and products was analyzed. The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel pipe, and the filling was 5% OV-101/80-100 mesh. The results of Chromosorb WAW-DMSC oxime reaction are as follows: Time (minutes) 10 20 30 40 50 60 70 Conversion ratio of gas to nitro group (%) 15.5 19.1 52.48 81.72 95.95 99.85 100 Selectivity of gas stupid amine 99.9% 99.9% 99.9% 99.9 % 99.9% 99.9% 99.9% Embodiment 9: Embodiment 4 catalyst, 2.54 g of p-nitrobenzene and 80 ml of methanol were placed in the reactor; the reaction system was first flushed with hydrogen for 10 minutes to remove the system. Air: first stir at low speed (about l rpm) and heat up To the reaction temperature of 10 (rc, while gradually pressurizing to a reaction pressure of 160 psig, when the temperature and pressure reach the reaction conditions, increase the stirring speed to 500 rpm, which is determined as the reaction start time 〇 = 〇); sampling every 1 minute 1342233 Once, when sampling, overflow the solution of about ίο drops to eliminate the error caused by the residual sample in the sampling tube; after the reaction is completed, 'stop the hydrogen supply, and then cool down and reduce the pressure; The chromatographic analyzer (China Chromatography 8700 F) was used to analyze the concentration of the reactants and the product. The chromatographic column was analyzed to be 3 m long, 1/8 inch diameter non-embroidered steel pipe, and the filling was 5% OV-101/ 80-100 mesh Chromosorb WAW-DMSC. The reaction results are as follows: Time (minutes) 10 20 30 40 50 60 70 80 nitro-substrate conversion rate (%) 11.5 26.5 60 78.21 89.2 96.51 99.66 100 p-aniline selectivity rate 99.9% 99.9%1 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% Embodiment 10: The embodiment 5 catalyst, 2.54 g of p-nitrobenzene and 8 ml of methanol are placed in the reactor, first with helium Rinse the reaction system for 10 minutes to remove air from the system First, stir at a low speed (about 100 rpm), and raise the temperature to a reaction temperature of 1 〇〇〇 c, while gradually pressurizing to a reaction pressure of 160 psig. When the temperature and pressure reach the reaction conditions, increase the mixing speed to 500 rpm. The start time of the reaction (1=〇); every 1 minute, the middle sampling-times 'sampling, first overflowing about 1G drops of the sample solution to eliminate the error caused by the residual sample liquid in the sampling tube; after the reaction is completed, stop The hydrogen is supplied, and the temperature is lowered and the pressure is reduced in turn; the sample is analyzed by the gas chromatograph analyzer (Chinese chromatography F), and the concentration of the reaction column is 3 meters long, and the diameter is 丨/8 shot. No_tube fill 1342233 is 5% OV-101/80-100 mesh Chromosorb WAW-DMSC. The reaction results are as follows: Time (minutes) 10 20 30 40 50 60 Gas-nitrol stupid conversion rate (%) 0.55 4.7 15.16 40.45 64.93 77.44 Selectivity of gas stupid amine 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% Time ( Minutes) 70 80 90 100 110 120 nitro-substrate conversion rate (%) 86.01 89.97 92.56 95.95 97.49 100 p-aniline selectivity rate 99.9% 99.9% 99.9% 99.9% 99.9% 99.9% The results of the above examples are shown in the first Figure. The first graph is a plot of the conversion of reaction to nitrobenzene and reaction time.