WO2000025912A1

WO2000025912A1 - A solid catalyst, its preparation and its application

Info

Publication number: WO2000025912A1
Application number: PCT/CN1999/000177
Authority: WO
Inventors: Caidong Qin
Original assignee: Caidong Qin
Priority date: 1998-11-04
Filing date: 1999-11-01
Publication date: 2000-05-11
Also published as: AU6459499A

Abstract

The present invention relates to a solid catalyst, its preparation and its application. The solid catalyst of this invention is based on a solid complex material comprising a film of aluminium oxide on the surface of metal aluminium or aluminium alloy, or aluminium oxide with a defective halite type structure. The catalyst of this invention can effectively activate the compounds composed of the element of carbon, hydrogen, oxygen, nitrogen, sulfur and chlorine. The catalyst can be used to effectively catalyze the reaction between nitrogen and hydrogen (the synthesis of ammonia), the decomposition of ammonia, and the reaction of nitrogen with hydrocarbons (the catalysis dehydrogenation with nitrogen as the oxidant), ammoxidation, or oxychlorination, and it can also be applied to the hydrogenation or the oxidation of the organic compound, the hydrolysis or the dehydration, and the electrolysis reaction of the synthesis of ammonia by electrolytic processes.

Description

一种固体催化剂，其制备方法及应用技术领域 Solid catalyst, preparation method and application thereof

本发明涉及一种固体催化剂，它是一种固体复合材料，包含附着在金属铝或铝合金上的氧化铝表面膜，或包含具有缺陷的岩盐结构的氧化铝的催化剂。本发明进一步涉及本发明固体催化剂的制备及在氨合成或氨分解、氮气与碳氢化合物反应、氨空气氧化反应、空气氧化反应、（空气)氧氯化反应、加氢反应、以及一氧化碳、二氧化碳、水参与的反应，含氧碳氢化合物的脱水反应等领域的应用。背景技术 The present invention relates to a solid catalyst, which is a solid composite material, a catalyst comprising an alumina surface film attached to metallic aluminum or an aluminum alloy, or an alumina having a defective rock salt structure. The invention further relates to the preparation of the solid catalyst of the invention and the synthesis or decomposition of ammonia, the reaction of nitrogen with hydrocarbons, the ammonia air oxidation reaction, the air oxidation reaction, the (air) oxychlorination reaction, the hydrogenation reaction, and carbon monoxide and carbon dioxide , Water-involved reactions, dehydration reactions of oxygenated hydrocarbons and other applications. Background technique

许许多多的有机化学品都是直接地或间接地取自地球上的自然资源如煤炭、天然气、石油等。这些资源基本上是由含有碳、氢、氧、氮、硫、氯元素所组成的共价化合物。因此，对于这些由碳、氢、氧、氮、硫、氯所组成的分子或化合物的催化反应，尤其是高效低温低压催化剂的发现和应用往往对于现代化工生产起着重要影响。 Many organic chemicals are taken directly or indirectly from natural resources on the earth, such as coal, natural gas, and oil. These resources are basically covalent compounds consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, and chlorine. Therefore, for the catalytic reactions of these molecules or compounds consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, and chlorine, especially the discovery and application of high-efficiency low-temperature and low-pressure catalysts often have an important impact on modern industrial production.

众所周知，催化材料是现代化学工业的关键。例如，由于铁系催化材料的发现和发展才有了今天的合成氨工业。但是由于目前合成氨所用催化剂必须在高温 (400— 500°C)和高压 (100-300大气压)下才比较有效，加上碳化物和硫化物极易使催化剂本身中毒失效，因此生产流程复杂，能耗高。 It is well known that catalytic materials are the key to the modern chemical industry. For example, due to the discovery and development of iron-based catalytic materials, today's ammonia synthesis industry. However, because the catalysts currently used to synthesize ammonia must be effective at high temperatures (400-500 ° C) and high pressures (100-300 atm), the addition of carbides and sulfides can easily poison the catalyst itself, so the production process is complex and can High consumption.

因此，寻找一种催化材料使之能够在低温低压的条件下实现氨的合成，并且能够直接让分子氮与天然气或者石油产品进行反应制取氨及有用的碳氢化合物，或者催化由这些碳、氢、氧、氮、硫、氯等元素组成的化合物的化学反应，必将能推动石油化工的进一步发展。本发明概述 Therefore, find a catalytic material to enable the synthesis of ammonia under low temperature and low pressure conditions, and directly react molecular nitrogen with natural gas or petroleum products to produce ammonia and useful hydrocarbons, or catalyze these carbon, Chemical reactions of compounds consisting of hydrogen, oxygen, nitrogen, sulfur, chlorine and other elements will definitely promote the further development of petrochemical industry. Summary of the invention

本发明涉及一种固体催化剂，它是一种固体复合材料，包含附着在铝或铝合金上的氧化铝表面膜，或包含具有缺陷的岩盐结构的氧化铝。 The present invention relates to a solid catalyst, which is a solid composite material including an alumina surface film attached to aluminum or an aluminum alloy, or an alumina having a defective rock salt structure.

本发明催化剂的复合材料进一步可含有选自元素周期表第 IA-VIA , IB- VIIB , VIII族或稀土元素中的一种或多种元素中的一种或多种元素，例如：钠，钾，镁，钙，钡，钇，钛，锆，钒，铬，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷，铋，硫或铈；这些元素以形成铝合金，铝的化合物，合金固溶体，氧化物和 /或单质的形态存在于复合材料中。本发明催化剂的复合材料还可含有空隙。 The composite material of the catalyst of the present invention may further contain one or more elements selected from one or more elements of the periodic table of the elements IA-VIA, IB- VIIB, group VIII or rare earth elements, for example: sodium, potassium , Magnesium, calcium, barium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, silicon, tin, phosphorus, bismuth, sulfur or cerium; these elements are based on Forms of aluminum alloys, aluminum compounds, alloy solid solutions, oxides, and / or elemental morphologies exist in composite materials. The composite material of the catalyst of the present invention may further contain voids. Gap.

本发明催化剂所包含的氧化铝中还可以掺杂有选自元素周期表第 IA-VIA , IB-VIIB , VIII族或稀土元素中的一种或多种元素的原子，例如钠，钾，镁，钙, 钡，钇，钛，锆，钒，铬，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷, 铋，硫或铈。 The alumina contained in the catalyst of the present invention may also be doped with an atom of one or more elements selected from the group consisting of Periodic Table IA-VIA, IB-VIIB, Group VIII or rare earth elements, such as sodium, potassium, magnesium , Calcium, barium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, silicon, tin, phosphorus, bismuth, sulfur or cerium.

本发明催化剂的制造方法包括下述步骤： The method for manufacturing the catalyst of the present invention includes the following steps:

A、称取金属铝粉或其合金粉， A. Weigh metal aluminum powder or its alloy powder,

C、对上述材料进行热处理或在含氧气氛下进行热烧结。 C. Heat treatment of the above materials or thermal sintering in an oxygen-containing atmosphere.

在步骤 A之后还可以包括步骤： Step A can also include steps:

B、在压力下将所述的铝粉或其合金粉压缩成型。 B. Compressing the aluminum powder or its alloy powder under pressure.

在步骤 C之后还可以包括步骤： Step C can also include steps:

D、进一步在氧化性化学溶液中对步骤 C所得到的材料进行化学或阳极氧化处理。 D. The material obtained in step C is further subjected to chemical or anodizing treatment in an oxidizing chemical solution.

其中步骤 D可以在步骤 C之后，也可以在步骤 A或 B之后。 Wherein step D may be after step C, or after step A or B.

本发明催化剂在制造过程步骤 C 中所述的热处理或热烧结温度可以在常温 The heat treatment or hot sintering temperature of the catalyst of the present invention in step C of the manufacturing process may be at ordinary temperature.

― 1300 。C的范围。 ― 1300. C range.

本发明催化剂的金属铝粉或其合金粉末中还可以加入元素周期表第 IA- VIA , IB-VIIB , VIII族或稀土元素中的一种或多种元素所组成的一种或多种物质粉末；其中所述的元素为钠，钾，镁，钙，钡，钇，钛，锆，钒，铬，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷，铋，硫或铈，当加人这些物质时，应首先进行均匀混合。 The metal aluminum powder or alloy powder of the catalyst of the present invention may also be added with one or more substance powders composed of one or more elements of Periodic Table IA- VIA, IB-VIIB, Group VIII or rare earth elements. ; The elements mentioned are sodium, potassium, magnesium, calcium, barium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, copper, zinc, boron, silicon, tin, phosphorus , Bismuth, sulfur or cerium, when adding these substances, they should be mixed uniformly first.

本发明经过热处理或热烧结的催化剂材料可以根据需要切割或破碎成各种尺寸和形状。 The heat-treated or heat-sintered catalyst material of the present invention can be cut or broken into various sizes and shapes as required.

本发明催化剂可以用以制备各种化合物，例如氨，胺，苯，氢气，氮气，水，一氧化氮，二氧化碳，三氧化硫，氢腈酸，腈类，碳氢化合物，碳氢氧化合物，含氮化合物，含硫化合物或含氯化合物。本发明的详细描述 The catalyst of the present invention can be used to prepare various compounds, such as ammonia, amine, benzene, hydrogen, nitrogen, water, nitric oxide, carbon dioxide, sulfur trioxide, nitrile acid, nitriles, hydrocarbons, carbon hydroxides, Nitrogen-containing compounds, sulfur-containing compounds or chlorine-containing compounds. Detailed description of the invention

本发明是关于使用附着在金属铝或铝合金上的氧化铝表面膜，或包含具有缺陷的岩盐结构的氧化铝为基础的复合材料作为新的催化剂，该催化剂的制造方法，及应用的发明。本发明的特点是此材料不仅能活化激活分子氮参与许多固氮的反应且能够活化主要由非金属元素 (在碳、氢、氧、氮、硫、氯元素之间所形成的)构成的化合物参与众多的化学反应。例如，氮气和氢气，或者氮气和天然气，氮气和石油原料制品反应制取氨及相关的新的碳氢、碳氢氧化合物。 The invention relates to a new catalyst using alumina surface film adhered to metal aluminum or aluminum alloy, or alumina-based composite material containing a defective rock salt structure, a method for manufacturing the catalyst, and an application invention. The feature of the invention is that this material can not only activate and activate molecular nitrogen to participate in many nitrogen-fixing reactions, but also can be activated mainly by non-metal elements (between carbon, hydrogen, oxygen, nitrogen, sulfur, and chlorine) ) Constitute compounds that participate in numerous chemical reactions. For example, nitrogen and hydrogen, or nitrogen and natural gas, and nitrogen react with petroleum raw materials to produce ammonia and related new hydrocarbons and carbon hydroxides.

本发明能够使一些非金属元素组成的化合物，尤其是碳、氢、氧、氮、硫、氯之间形成的化合物，被催化从而在较低温度和压力下进行化学反应。与现有的催化或未经催化的类似化学反应相比更具有经济和社会效益上的优势，因为相比之下，本发明所提供的催化剂有更高的耐催化剂的中毒以及更宽的使用范围。虽然目前许多的化工过程既可以用本发明的新催化剂也可以用现有的相应的催化剂产品，但现有催化剂多由贵重金属及过渡族金属组成，因此催化剂成本高且重金属易造成环境污染，而本发明的新催化材料可以不使用贵重金属或过渡族金属而只使用易得且无毒材料制成，因此不仅本发明的催化剂可以实现以前不能实现的催化反应，而且在代替现有催化剂的使用方面也具有明显的经济效益。 The present invention enables a compound composed of some non-metal elements, especially a compound formed between carbon, hydrogen, oxygen, nitrogen, sulfur, and chlorine, to be catalyzed to perform a chemical reaction at a lower temperature and pressure. Compared with the existing catalyzed or uncatalyzed similar chemical reactions, it has more economic and social benefits, because in comparison, the catalyst provided by the present invention has higher resistance to catalyst poisoning and wider use. range. Although many current chemical processes can use the new catalyst of the present invention or the existing corresponding catalyst products, the existing catalysts are mostly composed of precious metals and transition metals, so the catalyst costs are high and heavy metals are liable to cause environmental pollution. The new catalytic material of the present invention can be made of precious and non-toxic materials without using precious metals or transition group metals. Therefore, not only can the catalyst of the present invention realize catalytic reactions that could not be achieved before, but also replace existing catalysts. It also has obvious economic benefits in terms of use.

本发明描述了以金属铝为基础的复合材料用作催化剂的新发现及其应用方法和领域，但是，本发明权利要求所确定的范围并不意味或者限制本发明的使用范围。 The present invention describes new discoveries of metal-aluminum-based composite materials used as catalysts and their application methods and fields. However, the scope defined by the claims of the present invention does not imply or limit the scope of use of the present invention.

在本发明说明书书中，名词 "复合" 和 "复合材料" 系指二种或二种以上特性不同的结构及功能互补的物质的结合，这种结合不是简单的物质堆积，这种结合产生了结构上或功能上新的特性，而这种新的特性是原来任一单一物质所不具有的。名词 "铝合金"是泛指含有铝的合金 (包括与半金属形成的合金)。名词 "氧化铝膜"， "块状氧化铝" 是指两者晶体结构上的区别而不仅是形态上的区别。名词 "铝的无机化合物" 是指含铝的盐类或铝酸盐类化合物； "铝的金属间化合物" 是指铝与其它金属或半金属所形成的化合物；而 "铝的化合物" 系指前述的两种化合物的总称。 "名词 "激活" 或 "活化" 的使用是指所述催化剂能够使稳定的分子氮或其它反应物，或者本来不容易进行的化学反应变得更活泼，变得更容易进行。由于涉及到的许多化学反应依照条件，如反应温度、压力，停留时间的不同，可以有不同的反应产物或不同反应产物的分布，因此在本申请中未加区别主要反应或副反应或伴随的反应，主要展示了新催化材料对化学反应的有效催化能力。但这不影响在实际使用中可以结合已有的化学知识选择适当的反应条件，以实现不同产品的同时生产或所需产品的优化生产；或者以本申请中的主要催化活性物质为基础，对具体的催化反应还可以加入已知的具有催化活性的其它物质以进一步提高复合材料对该反应的催化活性，或加入已知对一具体催化反应的副反应有抑制的物质而提高对具体反应的选择性。复合催化材料的生产方法及分析 In the description of the present invention, the terms "composite" and "composite material" refer to a combination of two or more structurally and functionally complementary materials with different characteristics. This combination is not a simple matter accumulation. This combination produces Structurally or functionally new properties that are not present in any single substance. The term "aluminum alloy" refers generally to alloys (including alloys formed with semimetals) containing aluminum. The terms "alumina film" and "bulky alumina" refer to the difference in crystal structure, not just the difference in morphology. The term "inorganic compounds of aluminum" refers to salts or aluminate compounds containing aluminum; "intermetallic compounds of aluminum" refers to compounds formed by aluminum and other metals or semimetals; and "compounds of aluminum" refer to Generic term for the aforementioned two compounds. The use of "noun" or "activation" means that the catalyst can make stable molecular nitrogen or other reactants, or chemical reactions that are not easy to perform, more active and easier to perform. As it involves Many chemical reactions can have different reaction products or different reaction product distributions according to different conditions, such as reaction temperature, pressure, and residence time. Therefore, no distinction is made between the main reaction or side reaction or accompanying reaction in this application. The effective catalytic ability of the new catalytic materials for chemical reactions is not affected. However, it does not affect that in actual use, appropriate reaction conditions can be selected in combination with existing chemical knowledge to achieve simultaneous production of different products or optimized production of desired products; or Based on the main catalytically active substance in the present application, other substances with known catalytic activity may be added to the specific catalytic reaction to further improve the catalytic activity of the composite material for the reaction, or a known compound for a specific catalytic reaction may be added. Side reactions have inhibitory substances and increase the selectivity to specific reactions. Production method and analysis of composite catalytic materials

所述的催化材料特性及性能受制造过程及方法的影响。基本的制造过程主要包括称取粉末 (均匀混合)、压缩、热烧结三个过程；或者通过把氧化物或金属盐的粉末搅拌入熔融态的金属铝中，同时地或在搅拌后再行热烧结。 The characteristics and performance of the catalytic material are affected by the manufacturing process and method. The basic manufacturing process mainly includes three processes: powder weighing (uniform mixing), compression, and thermal sintering; or by stirring the powder of the oxide or metal salt into the molten metal aluminum, and then heating it simultaneously or after stirring sintering.

本发明所进行的实验中，不同成分的复合材料均被制作并单独地用于下文所说的应用之中，并且实验发现，这些复合材料均有下文所述的催化性能。这些复合材料分别由单纯的铝粉或铝粉与下列一种或数种粉末反应物质及少量的润滑剂，粘结剂或造孔剂均匀混合而制得 (粉末碾磨成小于 300微米的大小)。这些反应物有碳酸钾、氢氧化钾、碳酸钠、氢氧化钠、明矾、硼酸、氧化硅、氧化铋、氧化铝、氢氧化铝、氧化镁、碳酸钙、氧化钙、硫酸鈣、磷酸氢钙、磷酸铝、碳酸钡、氧化钇、氧化铬、氧化钼、氧化钨、氧化锆、氧化钒、氧化锰、氧化铁、氧化钴、氧化镍、氧化铜、氧化锌、硫酸铝、氧化锡、滑石粉 (含氧化镁及氧化硅)、氧化铈、镁、钛、钨、铁、镍、铜粉、及草木灰 (含硅、铝、镁、钾、钙、磷、铁等的氧化物)、或上述数种物质的混合物。其中碳酸钾、氢氧化钾，碳酸钠、氢氧化钠、氢氧化铝、硫酸铝、明矾、硼酸、氧化硅、磷酸铝、氧化铋、草木灰的含量分别为 5% (重量百分比)。其它种的混合物含有铝从 10%、 30%、 50%、 70%、至 90%的成分 (重量百分比，下同)。典型的组合物范例如：（1) 28%碳酸钙、 6% 氧化锌、 1 %碳酸钾、 1%滑石粉其余为铝粉；（2) 26%碳酸钙、 6%氧化锌、 3% 氧化铜、 1%碳酸钾、 1%滑石粉其余为铝粉；（3) 26%碳酸钙、 6%氧化锌、 4% 氧化镍、 1%碳酸钾、 1%滑石粉其余为铝粉；（4) 28%碳酸钙、 6%氧化锌、 3% 氧化锰、 1 %碳酸钾、 1%滑石粉其余为铝粉等等。从综合性能出发，实际应用时以上述由多种助催化物质所形成的复合材料为佳，比如，后者有更好的机械性能 In the experiments conducted by the present invention, composite materials with different components are made and used separately in the applications described below, and it is found experimentally that these composite materials have the catalytic properties described below. These composite materials are prepared by uniformly mixing pure aluminum powder or aluminum powder with one or more of the following powder reactive substances and a small amount of lubricant, binder or pore-forming agent (the powder is ground to a size of less than 300 microns) ). These reactants are potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, alum, boric acid, silicon oxide, bismuth oxide, aluminum oxide, aluminum hydroxide, magnesium oxide, calcium carbonate, calcium oxide, calcium sulfate, calcium hydrogen phosphate , Aluminum phosphate, barium carbonate, yttrium oxide, chromium oxide, molybdenum oxide, tungsten oxide, zirconia, vanadium oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, aluminum sulfate, tin oxide, talc Powder (including magnesium oxide and silicon oxide), cerium oxide, magnesium, titanium, tungsten, iron, nickel, copper powder, and plant ash (containing oxides of silicon, aluminum, magnesium, potassium, calcium, phosphorus, iron, etc.), or A mixture of the above. Among them, the content of potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, aluminum hydroxide, aluminum sulfate, alum, boric acid, silicon oxide, aluminum phosphate, bismuth oxide, and plant ash were 5% (weight percent). Other types of mixtures contain aluminum from 10%, 30%, 50%, 70%, to 90% (weight percent, the same below). Typical composition examples are: (1) 28% calcium carbonate, 6% zinc oxide, 1% potassium carbonate, 1% talc powder and the rest is aluminum powder; (2) 26% calcium carbonate, 6% zinc oxide, 3% oxidation Copper, 1% potassium carbonate, 1% talc powder and aluminum powder; (3) 26% calcium carbonate, 6% zinc oxide, 4% nickel oxide, 1% potassium carbonate, 1% talc powder and aluminum powder; (4) ) 28% calcium carbonate, 6% zinc oxide, 3% manganese oxide, 1% potassium carbonate, 1% talc powder and the rest is aluminum powder and so on. From the perspective of comprehensive properties, in practical applications, the composite materials formed by the above-mentioned various promoter materials are better. For example, the latter has better mechanical properties.

(空气气氛下 1000°C烧结 1小时时，压碎强度大于 20Mpa , 而仅由铝及碳酸钙所得材料为大于 5MPa), 及更好的耐水侵蚀能力。本文中优选的复合材料的组成是根据下列原因考虑的，如碳酸钙的加入是利用其高温时的热分解而使催化材料形成均匀的孔隙，氧化锌的加入是考虑到铝和锌可以形成具有机械强度的固溶体，因此，使催化剂有好的机械强度，钾的引入是根据巳知的事实，钾可以作为电子促进成分而促进催化反应，而氧化硅的引入可以使钾不易流失（《固体催化剂》，向德辉等著，化学工业出版社， 1983，第 147页)，以及镍具有加氢的能力，等等。这些都是在考虑到单独的铝与氧化钙或氧化锌可以形成所须的催化性能的基础上而可以采用的方法。当然，涉及到具体的催化反应，优选的复合材料的组成应考虑到具体反应对催化剂材质，催化性能方面的要求。复合材料在大于 5Mpa的压力下成型后经 700至 1300°C， 10-60分钟在空气气氛下烧结而成为灰色或灰褐色或灰黑色的固体材料，烧结温度和时间的选择应使复合材料具有一定的强度且剩有足量的金属铝；典型的烧结条件为 1000 C , 1 小时; 或 1 100°C， 45分钟，复合材料可以制成为任意形状，如粉末 (或附着在固体基体上的粉末)，颗粒，长条，或薄膜的形态。并且可以利用在铝的熔点以上容易对复合材料进行切割的特点，使烧结后的材料在冷却至铝的熔点以上温度时即进行切割成型为所须的尺寸。 (When sintered at 1000 ° C for 1 hour in air atmosphere, the crushing strength is greater than 20Mpa, while the material obtained only from aluminum and calcium carbonate is greater than 5MPa), and better resistance to water erosion. The composition of the preferred composite material is considered based on the following reasons. For example, the addition of calcium carbonate uses its thermal decomposition at high temperatures to form uniform pores in the catalytic material. The addition of zinc oxide is considered that aluminum and zinc can form Solid solution with mechanical strength, so that the catalyst has good mechanical strength. The introduction of potassium is based on the fact that potassium can be used as an electron-promoting component to promote the catalytic reaction, while the introduction of silicon oxide can make potassium not easy to lose ("Solid catalyst ", Xiang Dehui et al., Chemical Industry Press, 1983, p. 147), and nickel has the ability to hydrogenate, and so on. These are the methods that can be used in consideration of the required catalytic performance of aluminum and calcium oxide or zinc oxide alone. Of course, when it comes to specific catalytic reactions, the preferred composition of the composite material should take into account the requirements of the specific reaction on the catalyst material and catalytic performance. After molding the composite material under a pressure of more than 5Mpa, it will be sintered in air at 700 to 1300 ° C for 10-60 minutes to become a gray or gray-brown or gray-black solid material. The sintering temperature and time should be selected so that the composite has A certain strength and sufficient amount of metal aluminum left; typical sintering conditions are 1000 C, 1 hour; or 1 100 ° C, 45 minutes, the composite material can be made into any shape, such as powder (or adhered to a solid substrate) Powder), granules, strips, or films. In addition, the composite material can be easily cut above the melting point of aluminum, so that the sintered material can be cut to the required size when it is cooled to a temperature above the melting point of aluminum.

金相分析表明烧结而成的复合材料含有金属铝 (或铝合金)、氧化铝；当烧结混合物时，还有以铝为基础的金属间化合物或者铝酸盐相或铝盐相 (即铝的无机化合物)，或兼而有之，和 /或未完全与铝反应的剩余的反应物，该剩余反应物可以用作为助催化剂。 Metallographic analysis shows that the sintered composite material contains metal aluminum (or aluminum alloy) and alumina; when the mixture is sintered, there are also aluminum-based intermetallic compounds or aluminate or aluminum salt phases (that is, Inorganic compounds), or both, and / or the remaining reactants that have not completely reacted with aluminum, and the remaining reactants can be used as cocatalysts.

本发明实验发现在氮气气氛保护下烧结的复合材料其催化能力较弱，因此可以说明铝的氧化物在催化反应中起重要作用。 According to the experiment of the present invention, it is found that the composite material sintered under the protection of a nitrogen atmosphere has weak catalytic ability, so it can be explained that the aluminum oxide plays an important role in the catalytic reaction.

本发明实验发现未烧结的纯铝粉 (99.9%)也有较弱的催化作用，这说明金属铝起着主要的催化作用。可以设想，铝的化合物与铝的共存促进了铝的催化功能。由于铝与上述所列的物质均有下文所述的催化性能，这也说明这种催化活性是由于金属铝的存在。由于存放在空气中的铝粉或其在空气中所烧结的结果是金属铝 (或其合金)颗粒表面被一层薄的氧化铝膜所覆盖，说明铝的这种催化特性是铝和其表面氧化膜共同作用的结果。而由下文知，催化剂在铝的熔点以下或以上均能起催化作用，这表明铝的晶体结构即金属铝本身 (固体的或液体的)在催化时不起主要或本质的作用。可以认为铝金属或其合金主要起着支持氧化铝薄膜的功能。因此，可以断定这种复合催化材料中的主要催化活性物质是附着在金属铝或其合金表面上的氧化铝表面膜；或者可以说，具有这种晶体结构的氧化铝是本文所述的催化反应的催化活性物质。而目前这种特殊结构的氧化铝表面膜只发现存在于金属铝的表面（《无机化学丛书》，藏希文，汤卡罗等编，科学出版社， 1998 , 第 2卷, 第 458 页)，这种特殊结构是含有缺陷的具有岩盐结构的氧化铝。 According to the experiment of the present invention, it is found that unsintered pure aluminum powder (99.9%) also has a weak catalytic effect, which indicates that metallic aluminum plays a major catalytic role. It is conceivable that the coexistence of aluminum compounds and aluminum promotes the catalytic function of aluminum. Since aluminum and the substances listed above have the catalytic properties described below, this also indicates that this catalytic activity is due to the presence of metallic aluminum. Since the aluminum powder stored in the air or its sintering in the air results in the surface of metallic aluminum (or its alloy) particles being covered by a thin alumina film, this catalytic property of aluminum is that of aluminum and its surface The result of the combined action of oxide films. From the following, the catalyst can play a catalytic role below or above the melting point of aluminum, which indicates that the crystal structure of aluminum, that is, metal aluminum (solid or liquid) does not play a major or essential role in catalysis. It can be considered that aluminum metal or its alloy mainly functions to support an aluminum oxide film. Therefore, it can be concluded that the main catalytically active substance in this composite catalytic material is an alumina surface film attached to the surface of metallic aluminum or its alloy; or it can be said that alumina with such a crystal structure is the catalytic reaction described herein Of catalytically active substances. At present, the alumina surface film with this special structure is only found on the surface of metal aluminum (inorganic chemistry series, Tibetan Heiwen, edited by Tonkaro et al., Science Press, 1998, Vol. 2, p. 458) This special structure is alumina with a rock salt structure that contains defects.

当然，详细的催化机制有待做进一步的研究。但可以假设铝及其表面的氧化铝膜具有吸附并且能激活氮或其它非金属化合物的能力，及这种氧化铝膜具有强的固体酸-碱催化的特性。铝的金属间化合物或铝酸盐或铝盐化合物和 /或未完全与铝反应的反应物具有促进上述吸附能力及催化作用的功效，以及起到结构上使铝有更多催化表面的作用；或各成分之间的交互 /复合作用达到催化作用；如通过这些物质中的元素对氧化铝膜进行的类似半导体掺杂或引入缺陷的作用而促进催化功能或形成存在于铝表面的复杂结构的含铝化合物。当然，不排除存在于铝的金属间化合物内的铝元素所形成的氧化铝表面膜也具有与金属铝上的表面膜相类似的催化作用。 Of course, the detailed catalytic mechanism needs further research. However, it can be assumed that aluminum and the alumina film on its surface have the ability to adsorb and activate nitrogen or other non-metal compounds, and that this alumina film has strong solid acid-base catalyzed properties. Intermetallic compounds or aluminates or aluminum salt compounds of aluminum and / or reactants that do not fully react with aluminum have the effect of promoting the above-mentioned adsorption capacity and catalytic effect, and play a structural role in making aluminum more catalytic surface; Or the interaction / combination of the components to achieve catalytic effect; such as the semiconductor-like doping or defect-introducing effect of the alumina film by the elements in these substances to promote Aluminium-containing compounds that catalyze or form complex structures that exist on the surface of aluminum. Of course, it is not excluded that the alumina surface film formed by the aluminum element existing in the intermetallic compound of aluminum also has a catalytic effect similar to that of the surface film on aluminum metal.

因此，为了得到尽可能多的氧化铝表面膜以提高催化剂的活性，应适当减少其他物质的含量，即在保证催化效率和性能 (如空隙的大小和分布，选择性，稳定性等)的前提下尽可能提高氧化铝膜的含量，也可以在从液态铝 (或铝合金)制粉过程中，使粉末在含氧气氛下形成。以及把铝粉末制成片状以取得更大的比表面积。 Therefore, in order to obtain as much alumina surface film as possible to improve the activity of the catalyst, the content of other substances should be appropriately reduced, that is, the premise of ensuring catalytic efficiency and performance (such as the size and distribution of voids, selectivity, stability, etc.) In order to increase the content of the alumina film as much as possible, the powder can also be formed in an oxygen-containing atmosphere during the process of making powder from liquid aluminum (or aluminum alloy). And the aluminum powder is made into flakes to obtain a larger specific surface area.

由于金属铝与上述所列的物质均有下文所述的催化性能，因此进一步说明了作为这些复合材料所共有的成分氧化铝表面膜应是所说催化剂材料的主要活性物质。而助催化剂的选择和含量应根据具体的反应物，产物的分布，综合该反应对催化材料的机械的、热的稳定性及其它催化性能的要求，依已有的技术知识，进行常规的优化。 Since metallic aluminum and the substances listed above have the catalytic properties described below, it is further explained that the alumina surface film, which is a component common to these composite materials, should be the main active material of said catalyst material. The selection and content of the co-catalyst should be based on the specific reactants and product distributions, and comprehensively optimize the mechanical, thermal stability, and other catalytic performance requirements of the reaction materials for the catalyst, and perform conventional optimization based on existing technical knowledge. .

以复合材料在水中开始产生氨的时间长短来断定，实验发现，金属铝与氧化硅或硼酸所形成的催化材料效果较差。也许可以说明电负性比铝大的物质将不利于与铝形成本申请中所述的催化性能的材料。 Judging by the length of time that the composite material begins to produce ammonia in water, experiments have found that the catalytic material formed by metal aluminum and silica or boric acid is less effective. It may be stated that a substance having a greater electronegativity than aluminum will be detrimental to forming materials with aluminum that have the catalytic properties described in this application.

已知这种氧化铝表面膜与块状氧化铝有不同的结构和性质。由下文实验显示，这种表面氧化铝膜具有块状活性氧化铝的催化特性，因此可以代替已知用后者作催化剂的化学反应，典型的如催化脱水。但由于附着在铝上的氧化铝膜与块状氧化铝不同的特殊结构，前者为有缺陷的岩盐结构，后者为其它不相同的结构 (《无机化学丛书》，藏希文，汤卡罗等编，科学出版社， 1998 , 第 2卷，第 458 页)，其催化能力及范围不仅优于且与块状氧化铝有本质的区别，如氧化铝膜，尤其在铝粉与其它粉末混合烧结后，可以活化分子氮参与许多化学反应；但块状氧化铝未见报道可以明显活化分子氮参与化学反应，因此这种催化特性是原来意想不到的。而且，两种材料的制造方法也有本质的区别。所以，本发明克服了现有的或传统的在使用氧化铝作为催化剂的技术方案中仅限于使用块状氧化铝的局限，开拓了使用氧化铝表面膜作为催化剂的新的知识和新的应用领域。 It is known that this alumina surface film has a different structure and properties from a bulk alumina. The following experiments show that this type of surface alumina film has the catalytic characteristics of agglomerated activated alumina, so it can replace the known chemical reactions using the latter as a catalyst, typically such as catalytic dehydration. However, due to the special structure of the alumina film attached to aluminum, which is different from the bulk alumina, the former is a defective rock salt structure, and the latter is a different structure (Inorganic Chemistry Series, Tibetan Heiwen, Tangalo). (Eds., Science Press, 1998, Vol. 2, p. 458), its catalytic ability and range is not only superior to, but also fundamentally different from, bulk alumina, such as alumina films, especially when aluminum powder is mixed with other powders After sintering, molecular nitrogen can be activated to participate in many chemical reactions; however, it has not been reported that massive alumina can obviously activate molecular nitrogen to participate in chemical reactions, so this catalytic characteristic was unexpected. Moreover, there are essential differences in the manufacturing methods of the two materials. Therefore, the present invention overcomes the limitation of using alumina as a catalyst in the existing or traditional technical solutions that use alumina as a catalyst, and opens up new knowledge and new application fields of using alumina surface film as a catalyst. .

因此，该新催化剂具有氧化 -还原及酸-碱的双重催化特性或能力；在下文所给出的示范例中，的确证实了这种多功能的催化特性。 Therefore, the new catalyst has dual catalytic properties or capabilities of oxidation-reduction and acid-base; in the exemplary examples given below, such multifunctional catalytic properties are indeed confirmed.

所以本文所述复合材料基本可含有：金属铝 (或其合金)、附着在其上的氧化铝膜 (该膜应受到复合材料中加入的元素所掺杂)，块状的任一种形态的氧化铝，或进一步含有以铝为基础的铝的化合物、未完全反应的其它辅助物质 (这些辅助物质之间在高温的作用下可以形成合金固溶体，或这些辅助物质氧化为氧化物，或部分保持为单质的形态)。虽然上文所列混合物提供了制造这种催化剂复合材料的例子，但并不说明其它含金属铝的多项元素的混合物不可以用来制造类似功能的催化材料。金属铝或其合金可以以金属母相或颗粒形式存在于所述复合材料之中。此复合材料还含有 "空隙"，其存在可有效地增加催化剂的作用表面积，提高催化效率，通过控制原材料混合、压缩及热处理过程可以实现空隙大小及多少的控制。 Therefore, the composite material described in this article may basically include: metallic aluminum (or its alloy), an aluminum oxide film attached to it (the film should be doped with elements added in the composite material), and any of the bulk forms Alumina, or compounds further containing aluminum based aluminum, other auxiliary substances that are not fully reacted (these auxiliary substances Under the action of high temperature, solid materials can form alloy solid solution, or these auxiliary materials are oxidized to oxides, or part of them remain in the form of simple substance). Although the mixtures listed above provide examples of making such catalyst composites, it does not mean that other metal aluminum-containing multiple element mixtures should not be used to make similarly functional catalytic materials. Metallic aluminum or an alloy thereof may be present in the composite material in the form of a metal parent phase or particles. This composite material also contains "voids", the existence of which can effectively increase the surface area of the catalyst, improve the catalytic efficiency, and control the size and amount of voids by controlling the mixing, compression, and heat treatment of raw materials.

为了制造这种含有氧化铝表面膜的复合材料，或者进一步增加这种氧化铝表面膜的含量及厚度，还可以用化学的或电池的阳极氧化的方法得到实现。实验中，用饱和的高锰酸钾溶液浸泡金属铝粉 1小时，水洗后经 60°C烘干，其催化效果 (以催化氮气与氢气的反应作测试)明显优于纯铝粉，即在相同条件下，出口处气体的 pH更高；用饱和的高锰酸钾溶液浸泡烧结过的复合材料 (以 28%碳酸钙、 6%氧化锌、 1%碳酸钾、 1%滑石粉其余为铝粉经 1100°C， 45分钟烧结后所得的材料为例) 6小时，并经水洗晾干后，实验也发现其催化效果更好。因此，可以说明化学氧化可以促进氧化铝表面膜的形成和增加，并且，化学氧化可能使氧化铝表面膜变的更加凹弓不平，从而增加了催化反应的有效表面。由于化学氧化中水的存在，这种氧化铝表面膜由紧靠金属铝的氧化铝表面膜及外部的氧化铝水合物所组成（《铝的阳极氧化和染色》，黄奇松编著，香港万里书店出版，轻工业出版社重印， 1981，第 82页)，因此，在高温催化反应的使用条件下，氧化铝水合物脱水，将导致这种氧化铝表面膜由紧靠金属铝的氧化铝表面膜及外部的细小的氧化铝所组成，从而形成这种由氧化铝表面膜与细小的块状氧化铝的进一步的复合或形成具有复杂结构的表面氧化膜的催化材料。同理可以得出结论，这种氧化也可以用浓硫酸、或浓硝酸、或电池的阳极氧化来实现。 In order to manufacture such a composite material containing an alumina surface film, or to further increase the content and thickness of the alumina surface film, it can also be achieved by chemical or battery anodization. In the experiment, the saturated aluminum permanganate solution was used to soak the metal aluminum powder for 1 hour, and then washed with water and dried at 60 ° C. Its catalytic effect (tested by catalyzing the reaction between nitrogen and hydrogen) was significantly better than that of pure aluminum powder. Under the same conditions, the pH of the gas at the outlet is higher; soak the sintered composite material with saturated potassium permanganate solution (with 28% calcium carbonate, 6% zinc oxide, 1% potassium carbonate, 1% talc powder and the rest is aluminum The material obtained after sintering the powder at 1100 ° C for 45 minutes is an example.) After 6 hours of washing with water and drying, the experiment also found that its catalytic effect is better. Therefore, it can be explained that chemical oxidation can promote the formation and increase of the alumina surface film, and that chemical oxidation may make the alumina surface film more concave and convex, thereby increasing the effective surface of the catalytic reaction. Due to the presence of water in chemical oxidation, this alumina surface film is composed of an aluminum oxide surface film close to metal aluminum and an external alumina hydrate ("Anodic Oxidation and Dyeing of Aluminum", edited by Huang Qisong, published by Wanli Bookstore, Hong Kong (Reprinted by Light Industry Press, 1981, p. 82). Therefore, under the conditions of high temperature catalytic reaction, dehydration of alumina hydrate will cause this alumina surface film to be composed of alumina surface film close to metal aluminum and the outside. It is composed of fine alumina, so as to form this kind of catalytic material which is further composed of alumina surface film and fine bulk alumina or forms a complex surface oxide film. Similarly, it can be concluded that this oxidation can also be achieved by concentrated sulfuric acid, or concentrated nitric acid, or anodization of batteries.

其它方法，如将催化材料的粉末原料，如铝的合金粉末，在高温条件下氧化，再加人少量的纯铝粉作为粘结剂经低温 (大于铝的熔点温度)而压制成型。 Other methods, such as oxidizing powder raw materials of catalytic materials, such as aluminum alloy powder, under high temperature conditions, and adding a small amount of pure aluminum powder as a binder at a low temperature (greater than the melting temperature of aluminum) to press molding.

根据下文的实验结果，所说的以岩盐结构的氧化铝表面膜为主要活性物质的催化过程可以以氮气与氢气的反应为例说明如下，该过程与吴越在其《催化化学》（科学出版社， 1998，上册，第 382页)中关于氮分子在容易进行反应的化学体系中的氮固定路线相同： According to the experimental results below, the catalytic process using the alumina surface film of rock salt structure as the main active substance can be illustrated by taking the reaction of nitrogen and hydrogen as an example. (1998, Vol.1, p. 382) about the nitrogen fixation route of nitrogen molecules in chemical systems that are easy to react:

I . 氮气分子中的双原子同时附着在催化剂的表面上的特定位置并被活化，但不是形成两个离解了的氮原子 (因此，无需高的活化能)，即这种吸附是非解离的，而只是使得其部分价键处于失稳态，即削弱了氮分子的叁键，且此过程可以在常温常压条件下进行； I. The two atoms in the nitrogen molecule are attached to a specific position on the catalyst surface and activated at the same time, but not two dissociated nitrogen atoms are formed (hence, no high activation energy is needed), that is, this adsorption is non-dissociative But only make some of its valence bonds in an unstable state, which weakens the triple bond of the nitrogen molecule, and this process can Under normal temperature and pressure conditions;

II . 氢气分子中的双原子同时附着在催化剂的表面上的特定位置并被激活，可以是也可以不是形成两个可分离的激活的氢原子； II. The two atoms in the hydrogen molecule are attached to a specific position on the surface of the catalyst and activated at the same time, and may or may not form two separable activated hydrogen atoms;

III . 上述两个分子或四个原子如处在相邻位置，或附着了的氮气分子吸引气态中的氢原子或氢分子，通过氮氮之间三个键中的一个与两个氢成键则形成 III. If the above two molecules or four atoms are adjacent to each other, or the attached nitrogen molecules attract hydrogen atoms or hydrogen molecules in the gaseous state, one of the three bonds between nitrogen and nitrogen forms a bond with two hydrogens. Then formed

HN H (桥式端基结构)也即 N₂H₂的中间产物；按键能变化估算（《化学热力学》， (美)， I.M.克洛兹， R.M.罗森伯格著， 1972，鲍银堂，苏企华译， 1981 , 第 70 页)，此步为吸热过程。 HN H (bridged end structure) is also the intermediate product of N ₂ H ₂ Trans. 1981, p. 70). This step is an endothermic process.

IV . 上述中间产物 N₂H₂继续通过氮氮之间剩余的两个键中的一个与两个氢成键则形成 H₂NNH₂也即 N₂H₄的中间产物；按键能变化估算 (同上)，此步也为吸热过程。 IV. The above-mentioned intermediate product N ₂ H ₂ continues to pass through one of the two remaining bonds between nitrogen and nitrogen to form a bond with two hydrogens to form an intermediate product of H ₂ NNH ₂ , that is, N ₂ H ₄ ; Same as above), this step is also an endothermic process.

V . 上述中间产物 N2H4继续通过氮氮之间剩余的一个键与两个氢成键则形成¾ 11₃也即 N₂H₆的中间产物。此步为强放热过程（《有机化工原料大全》，魏文德主编，化学工业出版社， 1990 , 第 3卷，第 163页)。 V. The above-mentioned intermediate product N2H4 continues to form a ¾ 11 _3, which is an intermediate product of N ₂ H ₆ , through the remaining bond between nitrogen and nitrogen to form two hydrogen bonds. This step is a strong exothermic process (Encyclopedia of Organic Chemical Materials), edited by Wei Wende, Chemical Industry Press, 1990, Vol. 3, p. 163).

VI. N₂H₆的中间产物脱附为两个氨分子。 VI. The intermediate of N ₂ H ₆ is desorbed into two ammonia molecules.

而常规氮氢反应须经氮氮键的断裂或离解，形成中间产物 N 、 NH 、 NH₂ 而得产物氨（《催化化学》，吴越著，科学出版社， 1998 , 下册，第 997页)。 The conventional nitrogen-hydrogen reaction must break or dissociate the nitrogen-nitrogen bond to form the intermediate products N, NH, NH _{2 to} obtain the product ammonia ("Catalytic Chemistry", Wu Yue, Science Press, 1998, Vol. 2, p. 997) .

上述催化路径可以解释说明在室温条件下，水中通过电解或金属与水的反应产生氢原子时就有氨的生成，而不是氢与溶于水中的氧气反应生成热力学上更有可能的产物水，这是因为上述过程与常规的氮氢反应不同，上述过程无须氮氮三个键的完全断裂或氮分子的离解就可以实现催化反应，并且也说明该催化剂对氮气比对氧气有更强的催化活性。这是因为当由离解或游离的氢原子与吸附的氮反应时，上述步骤 (III), (IV), (V)全部将变为放热过程，即无须高温高压提供反应所须的能量，反应即可进行下去。自然地我们可以得出结论，氨合成可以在常温条件下，通过高电压电离解或光分解氢气或含氢化合物而产生离解或游离的氢原子与吸附的氮气分子的催化反应而实现。过程 (V)在一定温度范围内及高的临氢状态下可以认为是不可逆的自发过程。根据上述反应路径，氨合成的热力学平衡与使用金属催化剂 (如铁等)催化的情况应是不同的，也即高压和高温对氨合成反应速度和平衡都是有利的，并且由于反应 (IV)的产物 N₂H₄可以经反应 (V)得以转化，因此，氨合成的反应主要将不受热力学平衡的限制，反应动力学将是主要制约因素。工业应用上，氨合成的出口的氨含量将能实现大大的提高，从而将使氨与剩余合成气的分离实现减免，而可以使反应产物与二氧化碳直接反应生成碳酸氢氨。根据上述反应路径，在适当的氮氢比及温度和压力的条件下，将得到产物肼 (N₂ )。 The above catalytic path can explain that at room temperature, ammonia is generated when hydrogen atoms are produced by electrolysis or the reaction of metal and water in water, rather than the reaction of hydrogen with oxygen dissolved in water to produce thermodynamically more probable water, This is because the above process is different from the conventional nitrogen-hydrogen reaction. The above process can achieve the catalytic reaction without the complete break of the three bonds of nitrogen and nitrogen or the dissociation of nitrogen molecules, and also shows that the catalyst has a stronger catalysis for nitrogen than for oxygen. active. This is because when dissociated or free hydrogen atoms react with the adsorbed nitrogen, the above steps (III), (IV), (V) will all become exothermic processes, that is, it is not necessary to provide the energy required for the reaction at high temperature and pressure, The reaction can proceed. Naturally, we can conclude that ammonia synthesis can be achieved under normal temperature conditions by high-voltage ionization or photolysis of hydrogen or hydrogen-containing compounds to produce a dissociated or free hydrogen atom and a catalytic reaction of adsorbed nitrogen molecules. Process (V) can be considered as an irreversible spontaneous process in a certain temperature range and in a high hydrogen-prone state. According to the above reaction path, the thermodynamic equilibrium of ammonia synthesis should be different from the case of using metal catalysts (such as iron, etc.), that is, high pressure and high temperature are beneficial to the reaction rate and balance of ammonia synthesis, and due to the reaction (IV) The N ₂ H ₄ product can be converted by reaction (V). Therefore, the reaction of ammonia synthesis will not be limited by the thermodynamic equilibrium, and the reaction kinetics will be the main limiting factor. In industrial applications, the ammonia content at the outlet of ammonia synthesis can be greatly improved, so that the separation of ammonia from the remaining synthesis gas can be reduced, and the reaction product can directly react with carbon dioxide to form carbonic acid. Hydrogen ammonia. According to the above reaction path, under appropriate conditions of nitrogen-hydrogen ratio, temperature and pressure, the product hydrazine (N ₂ ) will be obtained.

因此，氮气加氢气的反应过程应可分为下面可逆及近似不可逆的两个部分： Therefore, the reaction process of nitrogen plus hydrogen should be divided into the following reversible and approximately irreversible parts:

N2、、 'N2H2、、N2H4 N2,, 'N2H2,, N2H4

N2H4 、'N2H6 、2(vJH3 如果说有缺陷的氧化铝表面膜具有优良的活化氮气分子的能力，那么有选择地在这种复合材料中加人对氢气有活化能力的过渡族金属，如镍等，则所形成的复合材料应对氮氢气的合成氨反应有更好的催化性能。 N2H4, 'N2H6, 2 (vJH3) If the defective alumina surface film has excellent ability to activate nitrogen molecules, then selectively add a transition metal such as nickel to this composite material that has the ability to activate hydrogen. Etc., the composite material formed should have better catalytic performance for the ammonia-hydrogen synthesis reaction.

上述催化路径也可以解释说明为什么在高温条件下 (如 850°C时)在空气 (含氮及氧气)携带水气时，虽然反应可以有氮气与氧气的反应及氮气与氢的反应 (氢产生于水与催化材料中的金属的反应或水的分解反应)，及氢与氧气的反应，但仍然有氨的生成而不是氮氧化物、水的生成，因为，依上述氮分子的活化及反应过程，有两个键的氧分子要与氮形成 ONNO 将涉及到两个氮氮键及氧氧键能量高的断裂过程。在临氧的条件下氮与氢能反应生成氨，而不是氧与氢反应生成水，说明该催化剂对氮的活化远较对氧的活化有效。这也从一个方面说明该催化剂能够实现氧气部分氧化的催化反应。依据上述催化过程模型，在复合催化剂中加人能对氧产生深度活化的成分，如 Fe , Co , Ni , Cr , Mn , Ti , Zn , Cr , Cd , Sn , Pb , Ce , Th等的氧化物 (《固体催化剂》，向德辉等著，化学工业出版社， 1983 , 第 165页)，将有利于氮气与氧气的直接反应；同理，加入能对氢气有效活化的组分将更有利于氮气与氢气的反应。进一步地可以推论，由于该催化剂对氧气的吸附活化弱于对氮气的活化，因此，对氧气的吸附也应是非解离的。而这种非解离的吸附氧能够使乙烯氧化为环氧乙烷 (《有机化工原料大全》，魏文德主编，化学工业出版社， 1990 , 第 2卷，第 207页)，所以，推测该催化剂也应可以用来催化乙烯或丙烯的氧气氧化生产环氧化物的反应。 The above catalytic path can also explain why under high temperature conditions (such as 850 ° C) when air (nitrogen and oxygen) carries water vapor, although the reaction can have a reaction of nitrogen and oxygen and a reaction of nitrogen and hydrogen (hydrogen production) (The reaction between water and the metal in the catalytic material or the decomposition reaction of water), and the reaction between hydrogen and oxygen, but there is still the formation of ammonia instead of nitrogen oxides and water, because according to the above-mentioned activation and reaction of nitrogen molecules In the process, the oxygen molecules with two bonds to form ONNO with nitrogen will involve the two nitrogen-nitrogen bond and the oxygen-oxygen bond high energy breaking process. In the presence of oxygen, nitrogen can react with hydrogen to form ammonia, but not oxygen and hydrogen to form water, which indicates that the catalyst for nitrogen activation is far more effective than oxygen activation. This also shows that the catalyst can achieve a catalytic reaction of partial oxidation of oxygen. According to the above catalytic process model, the composite catalyst is added with components that can deeply activate oxygen, such as the oxidation of Fe, Co, Ni, Cr, Mn, Ti, Zn, Cr, Cd, Sn, Pb, Ce, Th, etc. ("Solid Catalyst", Xiang Dehui et al., Chemical Industry Press, 1983, p. 165), will facilitate the direct reaction of nitrogen and oxygen; similarly, adding components that can effectively activate hydrogen will be more Facilitates the reaction between nitrogen and hydrogen. It can further be deduced that the adsorption of oxygen by this catalyst is weaker than the activation of nitrogen, so the adsorption of oxygen should also be non-dissociative. And this non-dissociated adsorbed oxygen can oxidize ethylene to ethylene oxide ("Encyclopedia of Organic Chemical Materials", edited by Wei Wende, Chemical Industry Press, 1990, Vol. 2, p. 207), so the catalyst is speculated It should also be used to catalyze the oxygen oxidation of ethylene or propylene to produce epoxides.

下面将主要地对由铝与 30%碳酸钙及 28%碳酸钙、 6%氧化锌、 1%碳酸钾、 1%滑石粉其余为铝粉 (空气气氛下 1000^QC烧结 1小时)制成的复合材料 (密度约为 1.8)的使用作一较全面的描述。由于催化反应效应类似，为描述简洁起见，其它种的复合催化材料的类似使用或者混合使用均免于写出。但从综合性能出发，实际应用应以由多种助催化物质所形成的复合材料为佳，比如它们有更好的机械性能，耐水侵蚀的能力等。 The following is mainly made of aluminum with 30% calcium carbonate and 28% calcium carbonate, 6% zinc oxide, 1% potassium carbonate, 1% talc powder and the rest is aluminum powder (1000 ^Q C sintered in air atmosphere for 1 hour). A more comprehensive description of the use of composite materials (with a density of about 1.8). Since the catalytic reaction effect is similar, for the sake of brevity of description, similar use or mixed use of other kinds of composite catalytic materials are exempt from writing. However, from the perspective of comprehensive performance, practical applications should be better with composite materials formed from a variety of co-catalysts. For example, they have better mechanical properties and resistance to water erosion.

使用铝及氧化钙 (由碳酸钙分解所得)制成的催化剂复合材料有助于避免实验中发现的催化特性与已知催化成分的作用相混淆，如铝与氧化镍的复合材料中由于镍也有加氢催化特性，这就使主要催化活性物质的判断变得困难，但由于金属铝、氧化钙及铝酸钙各自并不能 (也未见报道)用于相关催化领域 (例如合成氨反应中)，因此可以认定所发现的催化特性是主要由于氧化铝膜的作用，这一结论自然可以推及由铝与本文中所说其它成分组成的催化材料。复合材料的应用 Catalyst composites made of aluminum and calcium oxide (decomposed from calcium carbonate decomposition) help avoid experiments The catalytic properties found in this are confused with the role of known catalytic components. For example, in the composite materials of aluminum and nickel oxide, because nickel also has hydrogenation catalytic properties, this makes it difficult to judge the main catalytically active materials. Calcium oxide and calcium aluminate are not (and have not been reported) used in related catalysis fields (such as in ammonia synthesis). Therefore, it can be concluded that the catalytic properties found are mainly due to the role of alumina film. This conclusion can naturally be inferred. And catalytic materials composed of aluminum and other ingredients described herein. Application of composite materials

上述所说的复合催化材料用在了对以下几种物质在常温 -850°C 之间和常压下 (除 N₂和 H₂进行了加压试验外)的催化反应。这些物质包括：氮气、氢气、氧气、甲烷、一氧化碳、二氧化碳、氨、二氧化氮，多种碳氢及碳氢氧 (氮、硫、氯) 化合物、蒸馏水等。所用试剂除另有说明外均为分析纯、氮气、氢气、氧气、甲烷、一氧化碳、二氧化碳均由造气厂购得。实验条件下，反应所用空速在 200- 10000/h之间。提请注意的是在催化反应中所使用的实验参数仅作为参考而不是对今后使用的限定。在以下所有实施例中催化剂使用量为 200毫升，气体流量由气体流量计测出。除氮气加氢气使用合金钢制的高压反应器外，常压下的反应都是用石英玻璃管制的反应器。反应器内都装有本发明的催化剂。石英玻璃管由电阻丝加热，温度由插在颗粒状 (尺寸约 0.5-1厘米)催化剂中的热电偶读出。在本实验中如反应物为气体加液体则将该气体先通入液体或同时加热该液体再进人反应器，此时，气体同时起着携带气的作用；或者，将液体直接流人反应器；如反应物为气体加固体或半固体，则需加热这些固体、半固体物质，同时通人反应气体再进入反应器。各反应物的组成，除另有说明外，一般选在接近化学计量比的条件下，产物中气体的含量由吸收或吸收称重的方法或燃烧法等常规方法测出，物质含量的测量是所属化工行业工作者使用相应仪器设备可容易进行操作的。 The above-mentioned composite catalytic materials are used for the catalytic reaction of the following substances between normal temperature and -850 ° C and under normal pressure (except the pressure test of N ₂ and H ₂ ). These substances include: nitrogen, hydrogen, oxygen, methane, carbon monoxide, carbon dioxide, ammonia, nitrogen dioxide, a variety of hydrocarbons and hydrocarbon (nitrogen, sulfur, chlorine) compounds, distilled water and so on. Unless otherwise specified, all reagents used were analytical grade, nitrogen, hydrogen, oxygen, methane, carbon monoxide, and carbon dioxide were purchased from gas plants. Under the experimental conditions, the space velocity used in the reaction is between 200-10000 / h. It should be noted that the experimental parameters used in the catalytic reaction are for reference only and are not a limitation on future use. In all of the following examples, the amount of catalyst used was 200 ml, and the gas flow rate was measured by a gas flow meter. Except for high pressure reactors made of alloy steel for nitrogen and hydrogen, the reactions under atmospheric pressure are all reactors controlled by quartz glass. The reactor is filled with the catalyst of the present invention. The quartz glass tube is heated by a resistance wire, and the temperature is read by a thermocouple inserted in a granular (about 0.5-1 cm in size) catalyst. In this experiment, if the reactant is a gas plus a liquid, the gas is first passed into the liquid or the liquid is heated at the same time before entering the reactor. At this time, the gas also plays the role of carrying gas at the same time; or the liquid is directly flowed into the reaction If the reactant is a gas plus a solid or semi-solid, these solid and semi-solid materials need to be heated, and at the same time, the reaction gas is passed into the reactor. Unless otherwise specified, the composition of each reactant is generally selected under conditions close to the stoichiometric ratio. The gas content in the product is determined by conventional methods such as absorption or absorption weighing methods or combustion methods. The measurement of the substance content is The workers in the chemical industry can be easily operated by using the corresponding equipment.

为避免不需要的水份进入反应器，反应物在进入反应器之前先经氧化钙或无水氯化钙吸收水份。作为对比的实验或空白实验就不赘说于此文了。制备例 To prevent unwanted water from entering the reactor, the reactants absorb water through calcium oxide or anhydrous calcium chloride before entering the reactor. For comparison experiments or blank experiments, I will not go into details here. Preparation example

制备例 1 纯铝粉催化剂的制备 -1 Preparation Example 1 Preparation of Pure Aluminum Powder Catalyst -1

称取 500g的铝粉，放人饱和的高锰酸钾溶液中浸泡 1小时，取出放入水中进行洗涤，之后在 60 'C的烘箱中烘干。使用时以粉末的形态而应用。制备例 2 纯铝粉催化剂的制备 -2 500g of aluminum powder was weighed, soaked in a saturated potassium permanganate solution for 1 hour, taken out and washed in water, and then dried in a 60'C oven. It is applied in powder form during use. Preparation Example 2 Preparation of Pure Aluminum Powder Catalyst-2

称取 500g的铝粉， 5g淀粉，均匀混合后在模具中经约 25MPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 70(TC空气气氛下热烧结一小时而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 3 复合催化剂的制备 -1 Weigh 500g of aluminum powder and 5g of starch. After homogeneous mixing, they are formed into cylinders with a diameter of 50 mm and a thickness of 10 mm by a pressure of about 25 MPa in a mold. It is a catalytic material with voids. When used, it is cut into irregular particles with a size of about 0.5 cm. Preparation Example 3 Preparation of Composite Catalyst-1

称取 500g的铝粉， 125g的氧化铜粉， 10g淀粉，均匀混合后在模具中经约 20MPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 1000 'C空气气氛下热烧结一小时而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 4 复合催化剂的制备 -2 Weigh 500g of aluminum powder, 125g of copper oxide powder, 10g of starch, and mix them uniformly in a mold to form a cylinder with a diameter of 50mm and a thickness of 10mm under a pressure of about 20MPa, and then subject these cylinders to 1000 ° C air atmosphere. Heat sintered for one hour to form a voided catalytic material. When in use, it is cut into irregular particles about 0.5 cm in size. Preparation Example 4 Preparation of Composite Catalyst -2

称取 500g的铝粉， 100g的氧化镍粉， 30g淀粉，均匀混合后在模具中经约 lOOMPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 1300 'C空气气氛下热烧结 10分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 5 复合催化剂的制备 -3 Weigh 500g of aluminum powder, 100g of nickel oxide powder, 30g of starch, and mix them uniformly in a mold to form cylinders with a diameter of 50 mm and a thickness of 10 mm in a mold at a pressure of about 100 MPa. These cylinders were then subjected to a 1300 'C air atmosphere. Heat-sintered for 10 minutes to form a voided catalytic material. When used, it is cut into irregular particles of about 0.5 cm in size. Preparation Example 5 Preparation of Composite Catalyst -3

称取 800g的铝粉， 345g的碳酸钙粉， 10g淀粉，均匀混合后在模具中经约 Weigh 800g of aluminum powder, 345g of calcium carbonate powder, and 10g of starch.

120MPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 1000 °C空气气氛下热烧结 60分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 6 复合催化剂的制备 -4 A pressure of 120 MPa was formed into cylinders with a diameter of 50 mm and a thickness of 10 mm. These cylinders were then thermally sintered at 1000 ° C for 60 minutes to form void-shaped catalytic materials. When used, it is cut into irregular particles of about 0.5 cm in size. Preparation Example 6 Preparation of Composite Catalyst -4

称取 640g的铝粉， 280g的碳酸钙粉， 60g氧化锌粉， 10g碳酸钾粉、 10g 滑石粉， 50g淀粉， 50g乙醇，均匀混合后在模具中经约 50MPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 1000 °C空气气氛下热烧结 60 分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 7 复合催化剂的制备 -5 Weigh 640g of aluminum powder, 280g of calcium carbonate powder, 60g of zinc oxide powder, 10g of potassium carbonate powder, 10g of talcum powder, 50g of starch, 50g of ethanol, and mix them uniformly in a mold with a pressure of about 50MPa to form a diameter of 50mm. 10 mm cylinders, and these cylinders were then thermally sintered in an air atmosphere at 1000 ° C for 60 minutes to form a catalytic material with voids. When in use, it is cut into irregular particles about 0.5 cm in size. Preparation Example 7 Preparation of Composite Catalyst -5

称取 640g的铝粉， 280g的碳酸钙粉， 60g淀粉， 10g碳酸钾粉、 10g滑石粉， 50g淀粉， 50g石油醚，均匀混合后在模具中经约 50MPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 1100 °C空气气氛下热烧结 45分钟而成型为有空隙的催化材料。将这些经烧结所得材料放入饱和的高锰酸钾溶液中浸泡 6小时，取出人人水中进行洗涤，之后在 60 °C的烘箱中烘干。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 8 复合催化剂的制备 -6 Weigh 640g of aluminum powder, 280g of calcium carbonate powder, 60g of starch, 10g of potassium carbonate powder, 10g of talc powder, 50g of starch, 50g of petroleum ether, and mix them in a mold to form a diameter of 50mm and a thickness of 10mm by about 50MPa. These cylinders were then thermally sintered in an air atmosphere at 1100 ° C for 45 minutes to form a voided catalytic material. These sintered materials were immersed in a saturated potassium permanganate solution for 6 hours, taken out of human water for washing, and then dried in an oven at 60 ° C. When in use, it is cut into irregular particles about 0.5 cm in size. Preparation Example 8 Preparation of Composite Catalyst -6

称取 500g的铝粉， 25g的磷酸铝粉， 20g淀粉，均匀混合后在模具中经约 Weigh 500g of aluminum powder, 25g of aluminum phosphate powder, and 20g of starch.

50MPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 1100 °C空气气氛下热烧结 45分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 9 复合催化剂的制备 -7 50 MPa pressure was formed into cylinders with a diameter of 50 mm and a thickness of 10 mm. These cylinders were then thermally sintered in an air atmosphere at 1100 ° C for 45 minutes to form a catalytic material with voids. When used, it is cut into irregular particles of about 0.5 cm in size. Preparation Example 9 Preparation of composite catalyst -7

称取 100g的铝粉， 500g的氧化镍粉， 60g淀粉，均匀混合后在模具中经约 lOOMPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 800 °C空气气氛下热烧结 10分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 10 复合催化剂的制备 -8 Weigh 100g of aluminum powder, 500g of nickel oxide powder, and 60g of starch. After homogeneous mixing, they are formed into cylinders with a diameter of 50 mm and a thickness of 10 mm in a mold under a pressure of about 100 MPa. These cylinders are then subjected to 800 ° C air atmosphere. Heat-sintered for 10 minutes to form a voided catalytic material. When used, it is cut into irregular particles of about 0.5 cm in size. Preparation Example 10 Preparation of composite catalyst -8

称取 100g的铝粉， 500g的氧化钛粉， 60g淀粉，均匀混合后在模具中经约 lOOMPa的压力成型为直径 50mm，厚 10mm的圆柱体，再将这些圆柱体经 900 °c空气气氛下热烧结 10分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。制备例 11 复合催化剂的制备 -9 Weigh 100g of aluminum powder, 500g of titanium oxide powder, and 60g of starch. After homogeneous mixing, they are formed into cylinders with a diameter of 50 mm and a thickness of 10 mm in a mold under a pressure of about 100 MPa. These cylinders are then subjected to a 900 ° c air atmosphere. Heat-sintered for 10 minutes to form a voided catalytic material. When used, it is cut into irregular particles of about 0.5 cm in size. Preparation Example 11 Preparation of composite catalyst -9

称取 100g的铝粉， 500g的氧化镁粉， 100g氧化锰粉， 80淀粉，均匀混合后在模具中经约 lOOMPa的压力成型为直径 50mm , 厚 10mm的圆柱体，再将这些圆柱体经 900 °C空气气氛下热烧结 10分钟而成型为有空隙的催化材料。使用时再将其切割为约 0.5厘米大小的不规则的颗粒。实施例 Weigh 100g of aluminum powder, 500g of magnesium oxide powder, 100g of manganese oxide powder, 80 starch, and mix them uniformly into a mold with a pressure of about 100MPa to form a cylinder with a diameter of 50mm and a thickness of 10mm, and then pass these cylinders through 900 Heat-sintered for 10 minutes in an air atmosphere at ° C to form a voided catalytic material. When in use, it is cut into irregular particles about 0.5 cm in size. Examples

实施例 1：氮气和二氧化氮的反应 Example 1: Reaction of nitrogen and nitrogen dioxide

纯净的氮气 (99.8%)先通过盛有浓硝酸的容器，同时在容器中放人一铜片，所得氮气和二氧化氮的红棕色混合气体再进入反应器。在升温过程中，当温度超过 750°C 时，出口气由原来的可以使淀粉碘化钾试纸 (说明有二氧化氮的存在)变为只能使混有溴酸钾的淀粉碘化钾试纸 (说明有一氧化氮的存在，但无二氧化氮的存在)变为蓝紫色，这表明应发生了如下的反应： Pure nitrogen (99.8%) first passed through a container containing concentrated nitric acid. At the same time, a copper sheet was put in the container. The resulting red-brown mixed gas of nitrogen and nitrogen dioxide entered the reactor. During the temperature rising process, when the temperature exceeds 750 ° C, the outlet gas changes from the original starch starch potassium iodide test paper (indicating the presence of nitrogen dioxide) to the starch starch potassium iodide test paper (explaining the presence of nitric oxide) Presence, but without the presence of nitrogen dioxide) turns blue-purple, which indicates that the following reaction should occur:

N₂+NO₂ NO (1) N ₂ + NO ₂ NO (1)

或同时有： Or both:

NO₂ - NO+O₂ (2) NO ₂ -NO + O ₂ (2)

或进一步同时有下列反应： Or further have the following reactions at the same time:

NO₂ N₂+O₂ (3) 实施例 2 : 氮气和氢气的反应 NO ₂ N ₂ + O ₂ (3) Example 2: Reaction of nitrogen and hydrogen

纯净的氮气 (99.8%)和氢气 (99.5%)以 1 :3的体积比通过反应器。通过测量反应产物 pH值的变化以判定合成氨反应的进行。当温度达 250°C时，反应产物开始显碱性。随压力增加至 8个大气压 400°C条件下出口气 pH值达 11，氨含量达 1%。实验发现，随着温度的增加至 600°C , 出口气的 pH越来越大，达 13。 Pure nitrogen (99.8%) and hydrogen (99.5%) passed through the reactor in a volume ratio of 1: 3. The progress of the ammonia synthesis reaction was judged by measuring the change in the pH value of the reaction product. When the temperature reached 250 ° C, the reaction product became basic. With the pressure increasing to 8 atmospheres, the outlet gas has a pH value of 11 and an ammonia content of 1% at 400 ° C. The experiment found that as the temperature increased to 600 ° C, the pH of the outlet gas became higher and higher, reaching 13.

当与氮气及氢气同时通入约 10%的二氧化碳，实验发现氨合成仍在进行。这说明此催化材料不被二氧化碳所中毒。在实际氨合成条件下，由于二氧化碳、一氧化碳含量低，二氧化碳先转化为一氧化碳及水，经一氧化碳与氨反应转化为 HCN及水 (见下文的示例)，而 HCN由于加氢而转化为甲垸及氨。或者 CO与 H2 直接转化为甲烷等。或进一步地，甲垸通过脱氢逐步转化为高级的烃类而易于凝析并分离出合成气。实施例 3 : 氨分解反应 When about 10% of carbon dioxide was introduced at the same time as nitrogen and hydrogen, experiments found that ammonia synthesis was still ongoing. This shows that the catalytic material is not poisoned by carbon dioxide. Under actual ammonia synthesis conditions, due to the low content of carbon dioxide and carbon monoxide, carbon dioxide is first converted into carbon monoxide and water, which is converted into HCN and water by the reaction of carbon monoxide and ammonia (see the example below), and HCN is converted to formazan and hydrogen by hydrogenation. ammonia. Or CO and H2 are directly converted into methane and so on. Or further, formazan is gradually converted into advanced hydrocarbons by dehydrogenation, which is easy to condense and separate syngas. Example 3: Ammonia decomposition reaction

因为，一般地正反应的催化剂也是其逆反应的催化剂，实验中对氨的分解反应也进行了测试。含 25%氨的氨水经加热至起气泡后通入催化反应器，在 450°C 时，出口气可以点燃，但不能形成连续的火焰 (说明至少已有氢气的产生)；在大于 550°C时，出口气可以形成连续燃烧的火焰。因此，说明该催化剂在大于 450°C 时可以有效地催化氨的分解反应，并且，催化效果不受水气存在的影响。在温度大于 500°C时 (最高实验温度达 750°C), 用氨性铁氰化铜试剂检测出有肼的产生，即出口气使该试剂产生白色的混浊沉淀（《化学试剂配制手册》，楼书聪编著，江苏科学技术出版社， 1993，第 675页)，并也能使碱性的苦味酸试纸由黄色变为鲜红色，这应是肼在碱性条件下还原苦味酸为红色的二硝基氨基酚 (参见同上手册，第 639页)。用优级纯的氨水 (由上海振兴试剂二厂生产)代替上述分析纯的氨水进行实验，也得到相同的结果。该反应为： Because, generally, the catalyst of the positive reaction is also the catalyst of its reverse reaction, and the decomposition reaction of ammonia was also tested in the experiment. The ammonia water containing 25% ammonia is heated to bubble and then passed into the catalytic reactor. At 450 ° C, the outlet gas can be ignited, but cannot form a continuous flame (indicating that at least hydrogen has been generated); at greater than 550 ° C At this time, the outlet gas can form a continuously burning flame. Therefore, it shows that the catalyst can effectively catalyze the decomposition reaction of ammonia at a temperature higher than 450 ° C, and that the catalytic effect is not affected by the presence of water and gas. When the temperature is greater than 500 ° C (the maximum experimental temperature is 750 ° C), the ammonia ferricyanide reagent is used to detect the occurrence of hydrazine. That is, the outlet gas causes the reagent to produce a white turbid precipitate ("Handbook of Chemical Reagent Preparation", edited by Lou Shucong, Jiangsu Science and Technology Press, 1993, p. 675), and can also change the alkaline picric acid test paper from yellow For bright red, this should be dinitroaminophenol that reduces the picric acid to red under basic conditions (see ibid manual, page 639). The same results were obtained when the experiment was performed by using superior pure ammonia water (produced by Shanghai Zhenxing Reagent 2 Factory) instead of the analytical pure ammonia water. The response is:

NH₃ N₂H₄+H₂ (4) NH ₃ N ₂ H ₄ + H ₂ (4)

由于上述氨的直接分解方法的使用，肼的生产成本将会得到降低，因此肼必将会得到更广泛的使用，如作为储氢材料，或与二氧化碳反应生成肼基甲酸而作为代替尿素的肥料，或作为燃料电池的燃料用于驱动机动车辆，从而有助于减少由于燃油而造成的环境污染。 Due to the use of the above-mentioned direct ammonia decomposition method, the production cost of hydrazine will be reduced, so hydrazine will surely be used more widely, such as as a hydrogen storage material, or reacted with carbon dioxide to generate hydrazine formic acid as a fertilizer instead of urea Or used as fuel for fuel cells to drive motor vehicles, thereby helping to reduce environmental pollution caused by fuel oil.

上述结果也证实了在本申请中所提出的氮气与氢气反应合成氨的催化过程。同时，也说明合成气在高的氮气与氢气比的情况下，有可能在合成氨的同时直接地由部分合成气产生肼或主要地产生肼。 The above results also confirm the catalytic process for the synthesis of ammonia from the reaction of nitrogen and hydrogen proposed in this application. At the same time, it also shows that under the condition of high nitrogen-to-hydrogen ratio of syngas, it is possible to synthesize ammonia and produce hydrazine directly or mainly from hydrazine.

类似地将分析纯的氯化铵进行催化热分解，在反应温度大于 500°C时，其产物如上述情形也能使碱性的苦味酸试纸由黄色变为鲜红色，这说明发生了如下的反应： The analytically pure ammonium chloride is similarly subjected to catalytic thermal decomposition. When the reaction temperature is higher than 500 ° C, the product can also change the alkaline picric acid test paper from yellow to bright red as described above, which indicates that the following occurs: reaction:

NH₃ N₂H₄+H₂ (6) NH ₃ N ₂ H ₄ + H ₂ (6)

N₂H₄+HC1 N₂H₄«2HC1 (7) N ₂ H ₄ + HC1 N ₂ H ₄ «2HC1 (7)

总反应为： The total response is:

NH₄C1 N₂H₄»2HC1+H₂ (8) NH ₄ C1 N ₂ H ₄ »2HC1 + H ₂ (8)

上述过程由于可以使产生的肼稳定为盐酸肼，因此可以避免单纯肼的进一步的热分解。实验发现，碳酸氢氨也有类似上述的反应。实施例 4 : 氮气和碳氢化合物的反应 Since the above process can stabilize the generated hydrazine to hydrazine hydrochloride, further thermal decomposition of pure hydrazine can be avoided. Experiments have found that ammonia bicarbonate has a similar reaction. Example 4: Reaction of nitrogen and hydrocarbons

其中一例是氮气与甲垸 (1： 10的体积比)的反应。当反应器温度大于 250^eC 时，测得明显有氨的生成，测得出口气 pH值大于 8 , 600°C时测得氮的转化率大于 5%。对出口气进行分析发现不仅有氨的形成还有烯或炔烃的产物，这是因为出口气经水吸氨后可以快速地使 KMnO4溶液由紫红变为淡黄色。因此可以推断下列反应的进行： One example is the reaction between nitrogen and formamidine (1:10 volume ratio). When the reactor temperature is greater than 250 ^e C, it is obvious that ammonia is generated, and the outlet gas pH is measured to be greater than 8, and the nitrogen conversion rate is measured to be greater than 5% at 600 ° C. The analysis of the outlet gas found that not only the formation of ammonia but also the products of olefins or alkynes, because the outlet gas can quickly change the KMnO4 solution from purple red to pale yellow after absorbing ammonia through water. The following reactions can therefore be inferred:

N₂+CH₄ - NH₃+C₂H₄ (9)或 N ₂ + CH ₄ -NH ₃ + C ₂ H ₄ (9) or

N₂+CH₄ - NH₃+C₂H₂ (10)或 N ₂ + CH ₄ -NH ₃ + C ₂ H ₂ (10) or

N₂+CH₄ - NH₃+C (11) 其反应机制应是首先碳氢化合物脱氢形成游离的氢及 C-H自由基，而游离的氢与氮反应生成氨。 C-H自由基如 CH · · ·， CH2 · · , CH3 - 的重新组合分解及进一步脱氢从而可以形成新的化合物如乙烷、乙烯、丁烯、丁二烯、乙炔等。由于通常有机化学反应属于多级而又连续的反应，因此反应产物的分布与反应停留时间、温度、压力有关。当然，在更高的反应温度和压力下或许还可以实现下述催化反应： N ₂ + CH ₄ -NH ₃ + C (11) The reaction mechanism should be the dehydrogenation of hydrocarbons to form free hydrogen and CH radicals, and the free hydrogen reacts with nitrogen to form ammonia. CH radicals such as CH · · ·, CH2 · ·, CH3-are recombined and decomposed and further dehydrogenated to form new compounds such as ethane, ethylene, butene, butadiene, acetylene, etc. Because organic chemical reactions are usually multi-stage and continuous reactions, the distribution of reaction products is related to the reaction residence time, temperature, and pressure. Of course, the following catalytic reactions may be achieved at higher reaction temperatures and pressures:

N₂+CH₄ ^ NH₃+HCN (12) N ₂ + CH ₄ ^ NH ₃ + HCN (12)

由于由煤经合成气制甲垸是一较容易的生产过程；因此上述诸反应开辟了一条新的碳一化学途径。 Because the production of formazan from coal via syngas is an easier production process; the above reactions have opened up a new carbon-chemical pathway.

类似的具有相似特征的反应也发生在氮气和其它碳氢化合物之间。实验中使用了以下有代表性的物质，正已烷、环已烷、正庚垸、苯、甲苯、二甲苯、乙苯、石油液化气、石油醚、汽油、柴油、植物油 (菜子油)、液体石蜡、凡士林。实验发现正已烷、正庚垸、石油液化气、石油醚、汽油、柴油、植物油、液体石蜡、凡士林在 200°C 以上开始发生与氮气的反应，而环已烷在 250°C 时开始发生反应，苯、甲苯、二甲苯、乙苯在 400°C附近时即发生反应。反应生成物中除氨外 (氮的转化率一般大于 2%)还发现有烯烃、炔烃或有其它不饱和基团的碳氢化合物的生成。为了验证不饱和烃是由氮气参与的催化反应形成，石油液化气、石油醚、汽油、柴油、植物油先经浓溴水吸收不饱和烃类，油水分离干燥后再与氮气一起进入反应器。 Similar reactions with similar characteristics also occur between nitrogen and other hydrocarbons. The following representative substances were used in the experiment: n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, ethylbenzene, petroleum liquefied gas, petroleum ether, gasoline, diesel, vegetable oil (colza oil), Liquid paraffin, vaseline. The experiment found that n-hexane, n-heptane, petroleum liquefied gas, petroleum ether, gasoline, diesel, vegetable oil, liquid paraffin, petroleum jelly began to react with nitrogen above 200 ° C, and cyclohexane began to occur at 250 ° C The reaction occurs when benzene, toluene, xylene and ethylbenzene are around 400 ° C. In addition to ammonia (the nitrogen conversion rate is generally greater than 2%), olefins, alkynes, or hydrocarbons with other unsaturated groups have been formed in the reaction products. In order to verify that unsaturated hydrocarbons are formed by a catalytic reaction involving nitrogen, petroleum liquefied gas, petroleum ether, gasoline, diesel, and vegetable oil first absorb unsaturated hydrocarbons through concentrated bromine water, and then separate the oil and water into the reactor with nitrogen.

由上述实验结果，可以得出结论氮气与各种碳氢化合物在一定温度以上在复合催化材料的作用下可以进行以下的反应： From the above experimental results, it can be concluded that nitrogen and various hydrocarbons can perform the following reactions under the action of composite catalytic materials above a certain temperature:

N₂+C₆H₁₄ NH₃+C₆H₁₂ (或与其它 C-H化合物的混和物） (13)N ₂ + C ₆ H ₁₄ NH ₃ + C ₆ H ₁₂ (or mixture with other CH compounds) (13)

N₂+C₆H₁₂ → NH₃+C₆H₆(或与其它 C-H化合物的混和物） (14)N ₂ + C ₆ H ₁₂ → NH ₃ + C ₆ H ₆ (or mixture with other CH compounds) (14)

N₂+C₇H₁₆ → NH₃+C₇H₁₄ (或与其它 C-H化合物的混和物） (15)N ₂ + C ₇ H ₁₆ → NH ₃ + C ₇ H ₁₄ (or mixture with other CH compounds) (15)

N₂+C₆H₆ → NH₃+C₆H₅C₆H₅ (16)N ₂ + C ₆ H ₆ → NH ₃ + C ₆ H ₅ C ₆ H ₅ (16)

N₂+C₆H₅CH₃ → NH₃+C₆H₅CH₂CH₂C₆H₅ (或与多环 C-H化合物的混合 N ₂ + C ₆ H ₅ CH ₃ → NH ₃ + C ₆ H ₅ CH ₂ CH ₂ C ₆ H ₅ (or mixed with polycyclic CH compound

物） (17) (17)

N₂+C₆H₄(CH₃)₂ → NH₃+C₆H₅CH₂CH₃(或 C₆H₅-CH=C¾或其它化合物） (18)N ₂ + C ₆ H ₄ (CH ₃ ) ₂ → NH ₃ + C ₆ H ₅ CH ₂ CH ₃ (or C ₆ H ₅ -CH = C¾ or other compounds) (18)

N₂+C₆H₅CH₂CH₃ - NH₃+C₆H₅CH=CH₂(或其它化合物，如脱垸基后的苯） (19) 等等。 N ₂ + C ₆ H ₅ CH ₂ CH ₃ -NH ₃ + C ₆ H ₅ CH = CH ₂ (or other compounds, such as dephenylated benzene) (19) and so on.

上述的发生在氮气和碳氢化合物之间的此种反应可以概括为： The above-mentioned reaction that occurs between nitrogen and hydrocarbons can be summarized as:

N₂+CnHm →· NH₃+CnnHmm (20) 其中 CnnHmm是比 CnHm更高级的烃类或是碳链加长或数目增加的烃类化合物，或为裂解了的或环构化、苯环化了的烃类。如上文所述，类似的反应可以是多级连续的反应，因此所形成的碳氢化合物可以连续地与氮气反应；而最终产物或产物的分布受反应停留时间及温度，压力的影响。例如通过控制反应条件可以实现乙垸脱氢制乙烯再乙烯脱氢制乙炔、丁稀或丁二烯及氨的目的，而正已垸与氮气的催化反应可以生成乙烷、乙烯、丙垸、丙烯、丁垸、丁烯、丁二烯、已烯等以至于有腈类、胺类化合物的产生等。 N ₂ + CnHm → · NH ₃ + CnnHmm (20) Among them, CnnHmm is a higher-order hydrocarbon than CnHm or a hydrocarbon compound with a longer or increased carbon chain, or a cracked or ring-structured, benzene-cycled hydrocarbon. As mentioned above, similar reactions can be multi-stage continuous reactions, so the hydrocarbons formed can continuously react with nitrogen; and the final product or product distribution is affected by the reaction residence time, temperature, and pressure. For example, by controlling the reaction conditions, the purpose of dehydrogenation of acetamidine to ethylene and acetylene, butylene or butadiene and ammonia can be achieved by dehydrogenation of ethylene, and the catalytic reaction of hydrazone with nitrogen can produce ethane, ethylene, propane, Propylene, butadiene, butene, butadiene, hexene, etc. have the production of nitrile and amine compounds.

根据以上的反应 (20), 可以预见通过氮气对天然气、石油的氮气氧化处理，不仅可以得到有用的氨且同时可以实现对其加工制造新产品的目的。且由于氨的形成与单纯脱氢过程相反是一放热体积缩小的过程，因此在氮的作用下，天然气或石油制品的热裂解温度可以得到降低，并减少了压力对单纯热裂解的负作用。所以与常规石油裂解工艺相比，氮气不仅可以作为代替水蒸气的稀释气体且能通过氨的生成促进天然气、石油的裂解或脱氢裂解反应；又且由于可以降低反应温度，反应产物分布更易得到控制。而与氧气氧化脱氢过程相比氮气氧化脱氢不存在深度氧化生成水及二氧化碳的问题。当然由于氢含量的降低，氮气与重油或较重油的直接氮气氧化脱氢将易产生结焦或积炭，此时补以适当的水蒸气将可避免这种现象的发生。 According to the above reaction (20), it can be predicted that the nitrogen oxidation treatment of natural gas and petroleum by nitrogen can not only obtain useful ammonia but also achieve the purpose of processing and manufacturing new products. And because the formation of ammonia is a process of reducing the exothermic volume as opposed to the simple dehydrogenation process, the thermal cracking temperature of natural gas or petroleum products can be reduced under the action of nitrogen, and the negative effect of pressure on pure thermal cracking is reduced. . Therefore, compared with the conventional petroleum cracking process, nitrogen can not only be used as a diluent gas instead of water vapor, but also can promote the cracking of natural gas, petroleum, or dehydrocracking reaction through the generation of ammonia; and because the reaction temperature can be lowered, the distribution of reaction products is easier to obtain control. Compared with oxygen oxidative dehydrogenation, nitrogen oxidative dehydrogenation does not have the problem of deep oxidation to generate water and carbon dioxide. Of course, due to the reduction of the hydrogen content, the direct oxidative dehydrogenation of nitrogen with heavy oil or heavier oil will easily cause coking or coking. At this time, supplementing with appropriate water vapor will avoid this phenomenon.

另外，可以考虑天然气不经分离出甲垸而直接进行氮气氧化脱氢裂解生成烯烃类，如乙烯，丙烯等，所须的分离仅是对反应产物的分离，从而减少了对反应物的分离步骤，即降低了过程能耗。实施例 5 : 氮气和含氧或含氮碳氢化合物的反应由于含氧碳氢化合物如甲醇、乙醇、正丁醇、 ***、苯甲醇、苯乙醇等在催化剂的作用下有可能主要优先脱水而导致氮气与水及催化材料中的金属反应而产生氨等，因此，不易脱水的含氧碳氢化合物如丙酮、环已酮、环已醇分别用于与氮气的催化反应。实验发现当反应温度大于 200 °C时，均有相应醛或酮的生成 In addition, it can be considered that natural gas is directly subjected to nitrogen oxidative dehydrogenation and cracking to form olefins, such as ethylene, propylene, etc. without separation of formazan. The required separation is only the separation of reaction products, thereby reducing the steps of separating reactants. That reduces process energy consumption. Example 5: The reaction between nitrogen and oxygen-containing or nitrogen-containing hydrocarbons is because the oxygen-containing hydrocarbons such as methanol, ethanol, n-butanol, diethyl ether, benzyl alcohol, phenethyl alcohol, etc. may be mainly preferentially dehydrated under the action of a catalyst. As a result, nitrogen reacts with water and metals in the catalytic material to produce ammonia, etc. Therefore, oxygen-containing hydrocarbons such as acetone, cyclohexanone, and cyclohexanol, which are not easily dehydrated, are respectively used for the catalytic reaction with nitrogen. It was found that when the reaction temperature was higher than 200 ° C, the corresponding aldehydes or ketones were formed.

(由 2， 4-二硝基苯肼试剂检测出)以及有氨的形成 (出口气 pH值增加到 9)。因此可以相信有下列反应的发生： (Detected by the 2,4-dinitrophenylhydrazine reagent) and the formation of ammonia (the outlet gas pH increased to 9). Therefore it is believed that the following reactions occurred:

N₂ + (CH₃)₂CO → NH₃ + CH₂ = C = O + C₂H₄ (21)N ₂ + (CH ₃ ) ₂ CO → NH ₃ + CH ₂ = C = O + C ₂ H ₄ (21)

N₂ + C₆H₁₀O → NH₃ +苯酚或环烯酮或己烯酮（22)N ₂ + C ₆ H ₁₀ O → NH ₃ + phenol or cycloketenone or hexenone (22)

N₂ + C₆H₁₂0 → NH₃ + C₆H₅OH (苯酚）（23) 作为示范乙腈用于此类反应。实验发现氮与乙腈在 120°C以上时有强烈的氨形成，说明发生了以下的反应： N ₂ + C ₆ H ₁₂ 0 → NH ₃ + C ₆ H ₅ OH (phenol) (23) is used as an exemplary acetonitrile for such reactions. The experiment found that nitrogen and acetonitrile have strong ammonia when the temperature is above 120 ° C. The formation indicates that the following reactions have occurred:

N₂+CH₃CN → NH₃+NC(CH₂)₂CN (24)或N ₂ + CH ₃ CN → NH ₃ + NC (CH ₂ ) ₂ CN (24) or

N₂+CH₃CN → NH₃+NC(CH)₂CN (25)或N ₂ + CH ₃ CN → NH ₃ + NC (CH) ₂ CN (25) or

N₂+CH₃CN → NH₃+(CN)₂ (26) 类似的反应可以用于丙腈脱氢制丙烯腈或已二腈或氮气与含硫或含氯烃类的氮气氧化反应生成氨及更高级的含硫或含氯烃类的反应。实施例 6 : 加氢反应 N ₂ + CH ₃ CN → NH ₃ + (CN) ₂ (26) A similar reaction can be used for the dehydrogenation of propionitrile to acrylonitrile or acrylonitrile or nitrogen with the sulfur or chlorinated hydrocarbons. And more advanced sulfur or chlorinated hydrocarbon reactions. Example 6: Hydrogenation reaction

作为对各种官能团加氢的示范，加氢反应选用了苯、甲苯、二甲苯 (碳碳双键的加氢反应)，乙腈、硝基苯、硝基甲垸 (腈类及硝基化合物加氢制胺的反应)、及二硫化碳 (加氢脱硫的反应)，以及氯苯、四氯化碳 (加氢脱氯的反应), 羧酸加氢及丙酮临氨加氢的反应。 As an example of hydrogenation of various functional groups, benzene, toluene, xylene (carbon-carbon double bond hydrogenation reaction), acetonitrile, nitrobenzene, nitroformamidine (nitrile and nitro compound hydrogenation) were selected for the hydrogenation reaction. Reaction of hydrogen to amine), and carbon disulfide (hydrodesulfurization reaction), and chlorobenzene, carbon tetrachloride (hydrodechlorination reaction), carboxylic acid hydrogenation and acetone ammonia hydrogenation reaction.

当反应温度超过 400°C时，苯、甲苯、二甲苯发生加氢反应，其表现为反应产物使溴水完全脱色。这说明稳定的苯环已被加氢为含烯键的环，当然完全的加氢将导致环已垸环的形成，或苯环的裂开或垸基苯发生脱垸基反应，氢的转化率一般大于 10% (600°C时)。 When the reaction temperature exceeds 400 ° C, hydrogenation of benzene, toluene, and xylene occurs, which is manifested by the reaction product completely decolorizing the bromine water. This indicates that the stable benzene ring has been hydrogenated into an ethylenic ring. Of course, complete hydrogenation will lead to the formation of a ring, or the benzene ring is cleaved or the fluorenylbenzene undergoes a defluorination reaction. The conversion of hydrogen The rate is generally greater than 10% (at 600 ° C).

当反应温度达约 150°C以上时，乙腈的反应产物显碱性，其 pH值达 12，而 180°C以上时硝基苯及硝基甲垸加氢反应产物显碱性，其 pH达 12 , 氢的转化率大于 20%(400°C), 这说明有下列反应的发生： When the reaction temperature reaches about 150 ° C or higher, the reaction product of acetonitrile becomes alkaline, and its pH value reaches 12, and when it is above 180 ° C, the reaction product of nitrobenzene and nitroformamidine hydrogenation becomes basic, and the pH reaches 12, The conversion of hydrogen is greater than 20% (400 ° C), which indicates that the following reactions have occurred:

H₂+CH₃CN → CH₃CH₂N¾或 NH₃+C₂¾ H ₂ + CH ₃ CN → CH ₃ CH ₂ N¾ or NH ₃ + C ₂ ¾

C₆H₅NO₂+H₂ - C₆H₅NH₂ + H₂O C ₆ H ₅ NO ₂ + H ₂ -C ₆ H ₅ NH ₂ + H ₂ O

CH₃NO₂+H₂ -> CH₃NH₂ + H₂O CH ₃ NO ₂ + H _2- > CH ₃ NH ₂ + H ₂ O

或一般地， Or in general,

¾+CnHmN,O → CnHmmNA ¾ + CnHmN, O → CnHmmNA

当反应温度大于 200°C时，二硫化碳发生明显加氢反应，测得有硫化氢的生成，其余产物应为甲烷。可以相信其它含硫有机化合物也可以实现类似催化加氢反应。 When the reaction temperature is greater than 200 ° C, the carbon disulfide undergoes a significant hydrogenation reaction, and the generation of hydrogen sulfide is measured. The remaining product should be methane. It is believed that other sulfur-containing organic compounds can achieve similar catalytic hydrogenation reactions.

当反应温度大于 580°C时氢气与氯苯开始发生加氢脱氯反应。由于生成了氯化氢其产物 pH值达 1 , 其余产物应为苯、环己烯或环己垸，依加氢深度而定。 When the reaction temperature is higher than 580 ° C, hydrogen and chlorobenzene begin to undergo hydrodechlorination. Due to the formation of hydrogen chloride and the pH value of the product reached 1, the remaining products should be benzene, cyclohexene or cyclohexamidine, depending on the depth of hydrogenation.

而四氯化碳在 250°C时即开始发生加氢反应，生成氯化氢，其余反应产物应为三氯、二氯、一氯甲垸或甲烷，同样其最终反应产物、其分布依反应深度而定。 At 250 ° C, carbon tetrachloride begins to undergo hydrogenation reaction to generate hydrogen chloride. The remaining reaction products should be trichloro, dichloro, monochloromethane or methane. Similarly, the final reaction product and its distribution depend on the depth of the reaction. set.

由于含氯塑料如聚氯乙烯在热裂解时主要产物为氯化氢、碳氢化合物及苯的氯衍生物 (如氯苯等)。而该催化材料可以对有机氯、硫加氢脱除，说明在热裂解废旧塑料时不必分拣含氯或不含氯的塑料，可以同时经过热裂解 (热裂解时可以间断地通以水气或空气以加速热裂解过程)，除尘脱除酸性产物，加氢脱氯、硫及加氢饱和碳氢化合物，脱除酸性产物而得最终产物的过程。 Since the main products of chlorine-containing plastics such as polyvinyl chloride are hydrogen chloride, hydrocarbons and benzene during thermal cracking, Chlorine derivatives (such as chlorobenzene, etc.). The catalytic material can remove organic chlorine and sulfur by hydrogenation, which means that when pyrolyzing waste plastics, it is not necessary to sort plastics containing chlorine or non-chlorine, and it can also be subjected to thermal cracking at the same time. Or air to accelerate the thermal cracking process), dust removal to remove acidic products, hydrodechlorination, sulfur and hydrogenated saturated hydrocarbons, to remove the acidic products to obtain the final product.

作为示范，乙酸被用于加氢试验。实验时氢气通过盛有 36%的乙酸后进人反应器，或者将液态的乙酸流过催化剂 (类似于液相加氢的反应方法)。通过检测出口气体的 pH变化以判断加氢反应的开始，因为，酸性的乙酸加氢后变为中性的乙醛和 /或乙醇 (依反应停留时间而定)。实验发现在 350°C时，出口气 pH由 3增为 4.5 , 说明加氢过程已经开始。由于加氢反应是体积缩小的过程，因此在高压时起始反应温度应得到降低。当温度升为 680°C时，出口气 pH变为 7，说明加氢反应已经进行的完全，和 /或乙酸同时发生了完全的分解反应。可能的反应为： As a demonstration, acetic acid was used in the hydrogenation test. During the experiment, hydrogen was passed into the reactor after passing 36% acetic acid, or liquid acetic acid was passed through the catalyst (similar to the liquid-phase hydrogenation reaction method). The beginning of the hydrogenation reaction is determined by detecting the pH change of the outlet gas, because acidic acetic acid becomes neutral acetaldehyde and / or ethanol after hydrogenation (depending on the reaction residence time). The experiment found that the outlet gas pH increased from 3 to 4.5 at 350 ° C, indicating that the hydrogenation process has begun. Since the hydrogenation reaction is a process of reducing the volume, the initial reaction temperature should be reduced at high pressure. When the temperature rises to 680 ° C, the outlet gas pH becomes 7, indicating that the hydrogenation reaction has been completed and / or the complete decomposition reaction of acetic acid has occurred simultaneously. The possible responses are:

CH₃COOH+H₂ - CH₃CHO+H₂0 (31) CH ₃ COOH + H ₂ -CH ₃ CHO + H ₂ 0 (31)

或 CH₃COOH CH₂CO+H₂0 (32) Or CH ₃ COOH CH ₂ CO + H ₂ 0 (32)

CH₂CO+H₂ ^ CH₃CHO (33) CH ₂ CO + H ₂ ^ CH ₃ CHO (33)

CH₃CHO+H₂ CH₃CH₂OH (34) CH ₃ CHO + H ₂ CH ₃ CH ₂ OH (34)

利用此催化材料所具有的氨化、脱水和加氢的多功能催化特性，丙酮与氨及氢气进行了反应试验。当氢气分别携带丙酮及氨气，或丙酮与氨的混合液体流入反应器后，在温度大于 200^QC时，用 2 , 4-二硝基氯苯试剂检测出有胺的产生，即出口产物使该试剂变为黄色（《化学试剂配制手册》，楼书聪编著，江苏科学技术出版社， 1993 , 第 574页)。 Utilizing the multifunctional catalytic properties of ammoniation, dehydration and hydrogenation of this catalytic material, acetone was tested with ammonia and hydrogen. When hydrogen gas carries acetone and ammonia gas, or a mixed liquid of acetone and ammonia flows into the reactor, when the temperature is higher than 200 ^Q C, 2,4-dinitrochlorobenzene reagent is used to detect the production of amine, that is, the output product Make the reagent yellow ("Chemical reagent preparation manual", edited by Lou Shucong, Jiangsu Science and Technology Press, 1993, p.574).

由于新催化材料可以催化加氢及氮气氧化脱氢的反应，因此可以利用烃类碳氢化合物作为中间反应物的氮气氧化生成氨的反应 (20)结合对此产生的碳氢化合物再行加氢的反应，实现间接的氮与氢的氨合成反应。如选用乙垸、乙烯、或丙垸、丙烯，实现氮气氧化脱氢与加氢的循环。众所周知，高温低压有利于脱氢反应 (但应以不产生其它副反应为宜，尤其不宜产生加氢时不可再生为脱氢之前时的产物)；而低温高压有利加氢的反应 (但应考虑维持适当的反应速度为前提)。当然，中间反应物的选择也要考虑到循环操作的简单及高的脱氢和加氢能力的特性。 Since the new catalytic material can catalyze the reactions of hydrogenation and oxidative dehydrogenation of nitrogen, the reaction of nitrogen oxidation of hydrocarbons as intermediate reactants to generate ammonia (20) can be combined with the generated hydrocarbons for further hydrogenation Reaction to achieve an indirect ammonia synthesis reaction between nitrogen and hydrogen. For example, acetylene, ethylene, or propylene, propylene is used to realize the cycle of nitrogen oxidative dehydrogenation and hydrogenation. As we all know, high temperature and low pressure are favorable for dehydrogenation reaction (but it is advisable not to generate other side reactions, especially it is not suitable to produce products that are not regenerable before hydrogenation during hydrogenation); and low temperature and high pressure are favorable for hydrogenation reaction (but should be considered The premise of maintaining an appropriate reaction rate). Of course, the choice of intermediate reactants must also take into account the simplicity of the cycle operation and the characteristics of high dehydrogenation and hydrogenation capabilities.

上述氮气氧化脱氢与加氢反应可以分步进行，也可以氮、氢及上文所述的中间反应物同时进人反应器；由于化学平衡的要求，在适当的条件下，如中间反应物处在不饱和的价键状态，则首先将发生加氢反应，当反应进行到一定浓度时，氮气与所生成的处在饱和价态的中间反应物进行反应，使其回到平衡状态；从而出口物质主要包括氨、中间反应物、及未完全反应的氮及氢气。脱除氨后，这些物质可以进一步进行循环反应。也可以氮气、氢气及中间反应物同时进入反应器，但反应器分为先加氢及再脱氢反应器两部分，以便利于加氢及脱氢条件的同时优化。为进一步加强催化剂的加氢及脱氢性能，可以进一步增加在本文所述复合催化材料中的诸如镍的成份或其它已知有处理氢能力的催化物质。实施例 7 : 空气 (氧气)氧化碳氢或碳氢氧化合物的反应作为示范，垸烃中的甲烷、石油液化气 (市售，主要含有丙垸、丁垸、丙烯、丁烯)、正已垸、正庚垸、环已垸及芳烃中的苯、甲苯、二甲苯、乙苯、苯乙烯，碳氢氧化合物中的甲醇、乙醇被用于空气 (氧气)氧化的反应。 The above-mentioned nitrogen oxidative dehydrogenation and hydrogenation reactions can be carried out in steps, or nitrogen, hydrogen, and the above-mentioned intermediate reactants can enter the reactor simultaneously; due to the requirements of chemical equilibrium, under appropriate conditions, such as intermediate reactants In an unsaturated valence state, a hydrogenation reaction will first occur. When the reaction reaches a certain concentration, nitrogen reacts with the intermediate reactant in a saturated valence state to return it to an equilibrium state; Therefore, the outlet substances mainly include ammonia, intermediate reactants, and incompletely reacted nitrogen and hydrogen. After ammonia is removed, these materials can be further subjected to a cyclic reaction. Nitrogen, hydrogen, and intermediate reactants can also enter the reactor at the same time, but the reactor is divided into two parts: hydrogenation and dehydrogenation reactors to facilitate the optimization of hydrogenation and dehydrogenation conditions at the same time. In order to further enhance the hydrogenation and dehydrogenation performance of the catalyst, a component such as nickel or other catalytic substances known to have the ability to handle hydrogen in the composite catalytic materials described herein may be further added. Example 7: As an example, the reaction of air (oxygen) to oxidize hydrocarbons or carbon hydroxides is methane in thallium hydrocarbons, petroleum liquefied gas (commercially available, mainly containing propane, butylene, propylene, butene), Benzene, toluene, xylene, ethylbenzene, styrene in krypton, n-heptane, cyclohexylene, and aromatic hydrocarbons, and methanol and ethanol in carbohydrates are used for the oxidation of air (oxygen).

甲垸、甲醇和乙醇被用于空气 (氧气)氧化的催化反应。空气与甲烷的比例约为 5 : 1 , 甲醇、乙醇由空气经过后携带入反应器，空速均约为 1000/h。 Formamidine, methanol, and ethanol are used in the catalytic reaction of air (oxygen) oxidation. The ratio of air to methane is about 5: 1. Methanol and ethanol are carried into the reactor after passing through the air, and the space velocity is about 1000 / h.

当反应温度大于 450°C时，甲垸与空气的反应出口气可以使高锰酸钾紫色溶液产生沉淀及变色，也可以使铬酸试剂 (铬酸与硫酸的溶液)产生沉淀及变为蓝绿色，因此，可以判断有甲醇的产生（《化学试剂配制手册》，楼书聪编著，江苏科学技术出版社， 1993 , 第 693页)；同时，出口气也可以使硝酸银 Tollens试剂 (同上，第 518页)产生黑色沉淀，因此说明了有部分甲烷被进一步氧化为甲醛。实验发现依指示剂变化程度判断，在 450-550°C范围内甲醇及甲醛生成量最多，最佳反应温度应为 500°C 。 When the reaction temperature is greater than 450 ° C, the reaction outlet gas of formazan and air can cause precipitation and discoloration of the potassium permanganate purple solution, and can also cause the chromic acid reagent (a solution of chromic acid and sulfuric acid) to precipitate and turn blue. Green, therefore, it can be judged that the production of methanol ("Handbook of Chemical Reagent Preparation", edited by Lou Shucong, Jiangsu Science and Technology Press, 1993, p. 693); At the same time, the outlet gas can also use silver nitrate Tollens reagent (ibid., (P. 518) produces a black precipitate, thus indicating that some methane is further oxidized to formaldehyde. It was found from experiments that the amount of methanol and formaldehyde was the largest in the range of 450-550 ° C, and the optimal reaction temperature should be 500 ° C.

甲醇、乙醇的空气氧化在 450°C时，由硝酸银的 Tollens试剂测出有醛类的产生，该醛应分别为甲醛、乙醛。实验发现，最佳醛的生成温度约为 600°C。为了进一步地提高复合催化材料的上述甲醇氧化的活性，如在本申请中一贯所建议的，可以考虑用已知功能的催化剂与新催化材料作进一步的复合以进一步提高催化性能，即可以考虑用已知对甲醇空气 (氧气)氧化有优良催化活性的铁钼催化剂 (《有机化工原料大全》，魏文德主编，化学工业出版社， 1999，第 2版，中卷，第 122页)与本申请中的活性物质 (即通过在铁钼催化剂中加入金属铝而得到复合)，从而得到一种含有铁钼及附着在金属铝 (或其合金)表面上的氧化膜的复合催化剂。 When air oxidation of methanol and ethanol at 450 ° C, aldehydes were detected from Tollens reagent of silver nitrate. The aldehydes should be formaldehyde and acetaldehyde, respectively. The experiment found that the optimal aldehyde formation temperature was about 600 ° C. In order to further improve the above-mentioned methanol oxidation activity of the composite catalytic material, as has been consistently suggested in this application, it may be considered to further compound the new catalytic material with a catalyst with a known function to further improve the catalytic performance. An iron-molybdenum catalyst known to have excellent catalytic activity for methanol air (oxygen) oxidation ("Encyclopedia of Organic Chemical Materials", edited by Wei Wende, Chemical Industry Press, 1999, 2nd edition, middle volume, page 122) and in this application Active material (that is, compounded by adding metal aluminum to an iron-molybdenum catalyst), so as to obtain a composite catalyst containing iron-molybdenum and an oxide film attached to the surface of metal aluminum (or an alloy thereof).

石油液化气 (与空气的比例约为 1 :5)的空气氧化在温度即使增加达 750°C 时，出口气的 pH只呈现为弱酸性。在使人口的液化气经过溴水，高锰酸钾水溶液后，出口气在温度大于 300°C的情况下可以使高锰酸钾水溶液变色。这说明可能空气氧化产物中有烯烃或顺酐等的生成。其中正已垸、正庚垸在反应温度达 250°C时，反应开始呈酸性，随温度升高，反应产物酸性增加 pH值达 3(600°C), 说明酸性产物随温度增加含量有所增加。由于氧化过程中乙酸是最终较稳定的羧酸，所以产物中估计以乙酸为主要酸性产物，而其中间产物应是醇、醛类，当然不排除有酸酐的形成。反应中尤以高温时可以得到水汽及二氧化碳的产物。 The air oxidation of petroleum liquefied gas (the ratio of air to air is about 1: 5), even when the temperature increases up to 750 ° C, the pH of the outlet gas is only weakly acidic. After passing the population's liquefied gas through bromine water and potassium permanganate aqueous solution, the outlet gas can change the color of potassium permanganate aqueous solution at a temperature greater than 300 ° C. This indicates that olefins or maleic anhydride may be formed in the air oxidation products. Among them, when the reaction temperature reached 250 ° C, the reaction began to be acidic. With the temperature rising, the acidity of the reaction product increased to pH 3 (600 ° C), indicating that the content of acidic products increased with temperature. increase. Since acetic acid is the final relatively stable carboxylic acid during the oxidation process, it is estimated that acetic acid is the main acidic product in the product, and the intermediate products should be alcohols and aldehydes, of course, the formation of acid anhydride is not ruled out. The products of water vapor and carbon dioxide can be obtained especially at high temperature in the reaction.

环已垸在 150°C以上才开始形成酸性物质，其最小 pH值在 400 °C时为 4 , 随温度增加产物的酸性有所减弱。这说明在适度 (约 200°C)时有已二酸的形成，高温时主要产物为环已醇或环已酮 (由 2 , 4-二硝基苯肼试剂检测出)或有其它产物的生成。 The ring starts to form acidic substances when the temperature is above 150 ° C. Its minimum pH value is 4 at 400 ° C. The acidity of the product decreases with increasing temperature. This indicates that adipic acid is formed at a moderate temperature (about 200 ° C), and the main product is cyclohexanol or cyclohexanone (detected by 2,4-dinitrophenylhydrazine reagent) or other products at high temperature. generate.

苯、甲苯、二甲苯及苯乙烯产生酸性反应产物的起始温度分别为 450、 380、 The starting temperatures of benzene, toluene, xylene and styrene to produce acidic reaction products are 450, 380,

320及 380°C。随温度的升高，产物酸性增加，其 pH值达 4(除苯乙烯 600^QC时的反应产物 pH值达 3外)。根据已知的氧气氧化反应的结果，苯的氧化产物较复杂，可能含有苯酚，顺丁烯二酸酐或羧酸等。而甲苯应被主要地氧化成苯甲酸、二甲苯氧化为苯二甲酸及乙苯氧化为苯乙酸及苯甲酸，苯乙烯被氧化成苯甲酸或其它酸性物质，如辛二酸酐。 320 and 380 ° C. As the temperature increases, the acidity of the product increases, and its pH value reaches 4 (except that the reaction product pH value at styrene 600 ^Q C reaches 3). According to the results of the known oxygen oxidation reaction, the oxidation product of benzene is more complicated and may contain phenol, maleic anhydride or carboxylic acid. Toluene should be mainly oxidized to benzoic acid, xylene to phthalic acid and ethylbenzene to phenylacetic acid and benzoic acid, and styrene to benzoic acid or other acidic substances, such as suberic anhydride.

可以相信随反应温度的增加，最终都成为二氧化碳和水的燃烧反应。由于由铝组成的催化剂可以不含高温时 (如 iooo°c以上)的挥发性物质，且载体可以是稳定的氧化物，因而此催化材料将能用于高温催化燃烧装置中，或者将这种催化材料制成细小的颗粒 (如微米大小)加人燃油中，以实现催化燃烧。实施例 8 : 氨空气 (氧气)氧化反应 It is believed that as the reaction temperature increases, it eventually becomes a combustion reaction of carbon dioxide and water. Since the catalyst composed of aluminum may not contain volatile substances at high temperatures (such as above iooo ° C) and the carrier may be a stable oxide, the catalytic material will be used in a high-temperature catalytic combustion device, or the The catalytic material is made into fine particles (such as micron size) and added to the fuel to achieve catalytic combustion. Example 8: Ammonia air (oxygen) oxidation reaction

作为示范，碳氢化合物中的甲垸、液化石油气 (市售，主要含有丙垸、丁烷、丙稀、丁烯)、正庚垸、甲苯、二甲苯、苯乙烯，碳氢氧化合物中的甲醇、乙醇、丙酮、正丁醇被用于与氨及空气的氧化反应。所说反应的主要特点是有氢氰酸的生成，同时在与碳原子数多的化合物反应时应有高级的腈类生成，如乙腈，丙腈，丙烯腈，丁腈，芳香腈等的生成。实验中以检测出氢氰酸的生成为标志，作为判断氨空气氧化反应的开始。实验时，甲垸、液化气与空气分别以约等体积比进入氨水后再进入反应器，在涉及到液体反应物时，用两股等量空气分别进入 25%的氨溶液及上述溶液作为携带气再进人反应器。实验发现，甲垸在大于 550°C ; 液化气在大于 280°C ; 正庚垸在大于 250^eC；甲苯、二甲苯在大于 300°C ; 苯乙烯在大于 500°C；甲醇、乙醇在大于 250°C；丙酮在大于 300°C；正丁醇在大于 450^eC 时，氨氧化反应开始发生 (最高实验温度达 750°C)。反应过程涉及氧化脱氢，脱水，氨解和脱水，及碳碳键的断裂形成小分子化合物等。实施例 9 : 空气 (氧气)氧氯化反应 As examples, formazan in hydrocarbons, liquefied petroleum gas (commercially available, mainly containing propane, butane, acrylic, butene), n-heptane, toluene, xylene, styrene, carbon hydroxide Methanol, ethanol, acetone, and n-butanol are used in the oxidation reaction with ammonia and air. The main characteristic of the reaction is the formation of hydrocyanic acid. At the same time, when reacting with compounds with many carbon atoms, advanced nitriles should be formed, such as acetonitrile, propionitrile, acrylonitrile, butyronitrile, and aromatic nitrile. . In the experiment, the generation of hydrogen cyanide was detected as a mark, and the start of the ammonia air oxidation reaction was judged. In the experiment, formazan, liquefied gas and air enter the ammonia water at about equal volume ratios and then enter the reactor. When liquid reactants are involved, two equal amounts of air are used to enter the 25% ammonia solution and the above solution as a carry. Gas enters the reactor. The experiment found that formazan at more than 550 ° C; liquefied gas at more than 280 ° C; n-heptane at more than 250 ^e C; toluene and xylene at more than 300 ° C; styrene at more than 500 ° C; methanol and ethanol at Above 250 ° C; acetone above 300 ° C; n-butanol above 450 ^e C, the ammoxidation reaction begins to occur (maximum experimental temperature reaches 750 ° C). The reaction process involves oxidative dehydrogenation. Water, ammonolysis and dehydration, and the breaking of carbon-carbon bonds form small molecular compounds. Example 9: Air (oxygen) oxychlorination reaction

甲烷、液化石油气、正庚烷、甲苯被用于氧氯化反应的示范实验。甲烷、石油液化气与空气以约 4 : 1的比例进入反应器，浓盐酸 (含量 36%)由通过的空气携带入反应器。为检测方便，出口气经饱和的氢氧化纳和氢氧化钾溶液完全吸收未反应的盐酸 (即使出口气 pH接近 7)。 Methane, liquefied petroleum gas, n-heptane, and toluene were used as demonstration experiments in the oxychlorination reaction. Methane, petroleum liquefied gas and air enter the reactor at a ratio of about 4: 1, and concentrated hydrochloric acid (content 36%) is carried into the reactor by the passing air. For the convenience of detection, the unreacted hydrochloric acid is completely absorbed by the outlet gas through a saturated sodium hydroxide and potassium hydroxide solution (even if the outlet gas has a pH near 7).

甲垸用于空气氧氯化反应时，当反应温度大于 500°C , 点燃出口气所形成的火焰边缘显示有蓝绿色 (氯甲垸或氯乙垸的特征燃烧颜色，《有机化工原料大全》，魏文德主编，化学工业出版社， 1990 , 第 1卷，第 524 , 第 567页)，随温度增力口 (实验最高温度达 650°C), 这种蓝绿色的部分越来越多，并且，燃烧产物显酸性 (pH达 2), 因此可以说明有氯甲垸、氯乙烷或二氯乙垸的生成，且其含量随温度的增加而增加，其燃烧产物为二氧化碳、水及显酸性的盐酸。 When formazan is used in the air oxychlorination reaction, when the reaction temperature is above 500 ° C, the flame edge formed by igniting the outlet gas shows a blue-green (the characteristic burning color of chloroformamidine or chloroacetamidine, "Encyclopedia of Organic Chemical Materials" Edited by Wei Wende, Chemical Industry Press, 1990, Vol. 1, 524, p. 567), with increasing temperature (the highest temperature of the experiment reaches 650 ° C), more and more blue-green parts, and The combustion products are acidic (pH up to 2), so it can be explained that there is the formation of methyl formamidine, ethyl chloride or dichloroacetamidine, and its content increases with increasing temperature. The combustion products are carbon dioxide, water, and acidic. Of hydrochloric acid.

当石油液化气、正庚垸，或甲苯用于空气氧氯化反应时，当反应温度大于 350°C , 点燃出口气所形成的产物显酸性（pH达 2), 因此可以说明分别有含氯垸烃或氯烯烃，或氯甲苯或氯化苄等的生成。具体产物分布以正庚烷为例，可能有氯庚垸，氯甲垸，氯己垸，氯乙垸，氯戊垸，氯丁垸，氯丙垸或二氯烷烃等。同理，该催化剂也应可以实现具有重要工业意义的氧氯化乙烯生产氯乙烯的反应。 When petroleum liquefied gas, n-heptane, or toluene is used in the air oxychlorination reaction, when the reaction temperature is greater than 350 ° C, the products formed by igniting the outlet gas are acidic (pH 2), so it can be explained that each contains chlorine. Hydrocarbons or chloroolefins, or chlorotoluene or benzyl chloride. The specific product distribution is taken as an example of n-heptane, which may be chloroheptane, chloroform, chlorohexyl, chloroacetam, chloropentamidine, chloroprene, chloropropane, or dichloroalkane. In the same way, the catalyst should also be able to achieve the industrially significant reaction of oxychloroethylene to produce vinyl chloride.

由于空气中有大量的氮气，因此，上述氧氯化反应所生成的水将会与氮气及催化剂中的金属发生反应，生成碱性的氨，从而能导致氧化铝膜的溶解，造成催化剂的损耗。所以，上述的氧氯化反应应以纯的氧气为佳。实施例 10 硫化氢及二氧化硫的空气氧化反应由 HC1加入 Na₂S饱和水溶液中而产生的 H₂S与空气同时进入反应器，在反应温度为 500°C , 空速 500/h , 空气流量约为硫化氢的 20倍时，用碱性苦味酸钠试纸已检不出反应产物中有硫化氢的存在，说明硫化氢已完全被氧化，其产物应是水及二氧化硫及三氧化硫。但用氢氧化镍试纸不能检出反应产物中有明显的二氧化硫的存在，因此说明二氧化硫已完全被氧化为三氧化硫 (三氧化硫的检测用淀粉碘化钾试纸变为紫色而检测出)。类似的可以得出，其它含硫有机化合物也应可以有效地被催化氧化为三氧化硫及其它伴随的产物。实施例 1 1 : 一氧化碳与碳氢氧化合物的反应 Because there is a large amount of nitrogen in the air, the water generated by the above oxychlorination reaction will react with nitrogen and the metal in the catalyst to generate alkaline ammonia, which can cause the alumina film to dissolve and cause catalyst loss. . Therefore, the above oxychlorination reaction should preferably be pure oxygen. Example 10 Air oxidation reaction of hydrogen sulfide and sulfur dioxide H ₂ S produced by adding HC1 to a saturated aqueous solution of Na ₂ S enters the reactor simultaneously with air. At a reaction temperature of 500 ° C, a space velocity of 500 / h, an air flow rate of about When it is 20 times that of hydrogen sulfide, the presence of hydrogen sulfide in the reaction product has not been detected by the alkaline sodium picrate test paper, indicating that the hydrogen sulfide has been completely oxidized. The product should be water, sulfur dioxide, and sulfur trioxide. However, the presence of sulphur dioxide in the reaction product could not be detected with nickel hydroxide test paper, which indicated that the sulphur dioxide had been completely oxidized to sulphur trioxide (the starch trioxide potassium iodide test paper for sulphur trioxide detection was turned purple and detected). Similarly, it can be concluded that other sulfur-containing organic compounds should also be effectively catalyzed and oxidized to sulfur trioxide and other accompanying products. Example 11 1: Reaction of carbon monoxide with carbon hydroxide

在本例方法中，碳氢氧化合物选用了甲醇、乙醇、正丁醇、丙酮及***，作为示范实例。实验发现，当反应温度大于 350°C时，甲醇及乙醇， 280°C时丁醇、丙酮及***均有产物二氧化碳的产生（由 Ca(OH)₂水溶液形成碳酸钙沉淀检测出， 600 °C时一氧化碳的转化率一般大于 60%)。说明有下列反应发生： In the method of this example, the carbon hydroxide is selected from methanol, ethanol, n-butanol, acetone, and diethyl ether as exemplary examples. The experiment found that when the reaction temperature is higher than 350 ° C, methanol and ethanol, but at 280 ° C, butanol, acetone and diethyl ether all produce the product carbon dioxide (detected by the formation of calcium carbonate precipitation from aqueous Ca (OH) ₂ solution, 600 ° C The conversion rate of carbon monoxide is generally greater than 60%). The following reactions occurred:

CO+CnHmO → CnHm+CO₂ (35) CO + CnHmO → CnHm + CO ₂ (35)

或者含氧碳氢化合物先脱水形成相应的碳氢化合物后，由一氧化碳与水反应而生成二氧化碳的。实施例 12 : —氧化碳与水的反应 Or the oxygen-containing hydrocarbons are dehydrated to form the corresponding hydrocarbons, and then carbon monoxide is generated by the reaction of carbon monoxide with water. Example 12: Reaction of carbon oxide with water

当一氧碳通人冷水再进人反应器时，在反应温度大于 200°C时即可测出有明显的二氧化碳的生成，一氧化碳的转化率大于 5%(600°C时)，因此有下列催化反应： When monoxide is passed into the reactor and cold water enters the reactor, the formation of significant carbon dioxide can be measured when the reaction temperature is greater than 200 ° C, and the conversion rate of carbon monoxide is greater than 5% (at 600 ° C), so the following Catalytic reaction:

CO+H₂O - H₂+CO₂ (36) 实施例 13 : —氧化碳和氨的反应 CO + H ₂ O-H ₂ + CO ₂ (36) Example 13: —Reaction of Carbon Oxide and Ammonia

当一氧化碳通过氨水 (含 25%氨)再进入反应器时，当反应温度超过 320°C 时，即测得有氢氰酸的形成，一氧化碳的转化率大于 30%(600^QC 时)。显示方法是用碱性苦味酸钠试纸，当遇有氢氰酸时，试纸由黄色变为深红色。并使用了使氯化铁，硫代硫酸钠，氨的水溶液由深兰变为粉红色 (由于氢氰酸与硫代硫酸钠，反应产生了硫氰酸根离子而生成了红色的硫氰酸铁的缘故)的方法进行了进一步的验证。因此我们有下列反应： When carbon monoxide enters the reactor through ammonia water (containing 25% ammonia), when the reaction temperature exceeds 320 ° C, the formation of hydrocyanic acid is measured, and the conversion rate of carbon monoxide is greater than 30% (at 600 ^Q C). The display method is to use alkaline sodium picrate test paper. When encountering hydrocyanic acid, the test paper changes from yellow to dark red. And the use of ferric chloride, sodium thiosulfate, ammonia solution from dark blue to pink (due to the reaction of hydrocyanic acid and sodium thiosulfate, thiocyanate ion was generated to produce red iron thiocyanate The reason) is further verified. So we have the following reactions:

CO+NH₃ → HCN+H₂O (37) CO + NH ₃ → HCN + H ₂ O (37)

上述该反应首先应是形成甲酰胺 (HCONH₂), 甲酰胺再经高温分解为 HCN和 H₂O。因此在低温高压时可能得到甲酰胺的产物。 The above reaction should first form formamide (HCONH ₂ ), and formamide is decomposed into HCN and H ₂ O by high temperature. Therefore, the product of formamide may be obtained at low temperature and high pressure.

由于 HCN可以经有氧水解转化为氨、尿素及甲酸，因此 HCN可以得到更多的用处。实施例 14 : 一氧化碳与二氧化氮的反应 Since HCN can be converted into ammonia, urea and formic acid by aerobic hydrolysis, HCN can be used more. Example 14: Reaction of carbon monoxide and nitrogen dioxide

在实验中二氧化氮如前述的铜加浓硝酸的方法制得。当一氧化碳携带红棕色的二氧化氮通过反应器时，当反应温度大于 200°C时，二氧化氮红棕色消失，同时测得有二氧化碳的生成，故有以下反应： CO+NO₂ → N₂+CO₂ (38) Nitrogen dioxide was obtained in the experiment as described above with copper and concentrated nitric acid. When carbon monoxide passes red-brown nitrogen dioxide through the reactor, when the reaction temperature is greater than 200 ° C, the red-brown nitrogen dioxide disappears, and the formation of carbon dioxide is measured. Therefore, the following reactions occur: CO + NO ₂ → N ₂ + CO ₂ (38)

可以相信有相似的反应 Can believe a similar response

CO+NOx - N₂+CO₂ (39) CO + NOx-N ₂ + CO ₂ (39)

类似地也可以有 CO与 SOx之间的反应。实施例 15 : 氨与氮氧化物的反应 Similarly there can be reactions between CO and SOx. Example 15: Reaction of ammonia with nitrogen oxides

使氮气分别通过氨水和硝酸后，氮气中携带氨、氮氧化物后通过无水氯化钙除去水分后进人被加热的催化材料，在温度大与 350°C时，可以见到明显的水汽的生成，在大于 600 C时，用硫脲试剂（《化学试剂配制手册》，楼书聪编著，江苏科学技术出版社， 1993，第 707页)已测不出有二氧化氮的存在 (注：二氧化氮与水反应产生产物之一亚硝酸)。说明了氨与氮氧化物进行了以下的反应： NH₃+NOx → N₂+H₂O (40) 实施例 16：一氧化碳与空气 (氧气)的反应 After passing nitrogen gas through ammonia water and nitric acid, the nitrogen gas carries ammonia and nitrogen oxides, and then passes through anhydrous calcium chloride to remove water and enter the heated catalytic material. When the temperature is higher than 350 ° C, obvious water vapor can be seen. The formation, at more than 600 C, using thiourea reagent ("Chemical Reagent Preparation Manual", edited by Lou Shucong, Jiangsu Science and Technology Press, 1993, p. 707) has not detected the presence of nitrogen dioxide (Note: Nitrogen dioxide reacts with water to produce one of the products, nitrous acid). The following reaction between ammonia and nitrogen oxides is illustrated: NH ₃ + NOx → N ₂ + H ₂ O (40) Example 16: Reaction of carbon monoxide with air (oxygen)

约 2%体积比的一氧化碳与空气混合进入反应器，当反应温度大于 200°C时，即测得有二氧化碳的产生，该反应是： About 2% by volume of carbon monoxide is mixed with air into the reactor. When the reaction temperature is greater than 200 ° C, the generation of carbon dioxide is measured. The reaction is:

CO+O₂(空气） → CO₂ (41) CO + O ₂ (air) → CO ₂ (41)

以上反应表明此复合催化材料可以用于对汽车及其它燃烧装置的尾气的催化净化处理。其中反应 (40)中所须氨的生成可以经尾气中的氮气与水气及催化材料中的金属在现场反应而得。实施 17 : —氧化碳、水及硝基化合物的反应使一氧化碳、水及硝基苯三者通人反应器，温度大于 250°C时，即测得出口处的气体的 pH值约为 11，同时有二氧化碳生成。因此说明发生了一氧化碳与水生成氢气及二氧化碳，所生成的氢气与硝基苯反应生成苯胺的过程；当一氧化碳与水及硝基甲垸三者同时通入反应器，在 300°C时即测出有碱性的甲胺的生成。此例说明在适当条件下加氢反应可以用一氧化碳及水代替氢气以实现加氢的反应，如不饱和碳氢化合物、硝基化合物、含硫、氯化合物的加氢等。实施例 18 : —氧化碳与氢气的反应 The above reactions indicate that this composite catalytic material can be used for the catalytic purification treatment of exhaust gases from automobiles and other combustion devices. Among them, the required ammonia generation in reaction (40) can be obtained by reacting nitrogen in the tail gas with water gas and metals in the catalytic material on site. Implementation 17:-The reaction of carbon oxide, water and nitro compounds makes the three of carbon monoxide, water and nitrobenzene pass into the reactor. When the temperature is greater than 250 ° C, the pH value of the gas at the outlet is measured to be about 11, At the same time, carbon dioxide is generated. This shows that carbon monoxide and water generate hydrogen and carbon dioxide, and the generated hydrogen reacts with nitrobenzene to form aniline. When carbon monoxide, water, and nitroformamidine are simultaneously passed into the reactor, it is measured at 300 ° C. The formation of basic methylamine. This example shows that under appropriate conditions, carbon monoxide and water can be used instead of hydrogen to achieve hydrogenation reactions, such as hydrogenation of unsaturated hydrocarbons, nitro compounds, sulfur-containing compounds, and chlorine compounds. Example 18: Reaction of Carbon Oxide and Hydrogen

当一氧化碳与氢气同时通人反应器时，在温度大于 200°C的条件下 (实验最高温度达到 550°C), 反应产物可以快速地使高锰酸钾溶液脱色并形成沉淀物，同时也可以使铬酸试剂 (铬酸与硫酸的溶液，《化学试剂配制手册》，楼书聪编著，江苏科学技术出版社， 1993 , 第 693页)产生沉淀及变色。作为对比，未经反应器的该混合气体或未经催化剂催化但加热到同样温度的混合气体通气时间数倍增长的条件下，也不能使这些溶液产生沉淀物或脱色。因此说明经过本发明催化反应的产物有甲醇，或由甲醇脱水生成的甲醚或由甲醚进一步脱水生成的乙烯等。考虑到此催化材料所具有的良好的耐毒性，它的应用将进一步降低由煤制碳氢或碳氢氧化合物的成本。实施例 19 : 烷基芳香烃脱垸基反应 When carbon monoxide and hydrogen are introduced into the reactor at the same time, the reaction product can quickly decolorize the potassium permanganate solution and form a precipitate at a temperature greater than 200 ° C (the maximum temperature of the experiment reaches 550 ° C). It is also possible to cause precipitation and discoloration of chromic acid reagents (solutions of chromic acid and sulfuric acid, Manual of Chemical Reagent Preparation, edited by Lou Shucong, Jiangsu Science and Technology Press, 1993, p.693). In contrast, under the condition that the aeration time of the mixed gas without the reactor or the mixed gas heated to the same temperature without being catalyzed by the catalyst increases several times, these solutions cannot cause precipitation or discoloration of the solutions. Therefore, it is shown that the products undergoing the catalytic reaction of the present invention include methanol, methyl ether produced by dehydration of methanol, or ethylene produced by further dehydration of methyl ether, and the like. Taking into account the good toxicity resistance of this catalytic material, its application will further reduce the cost of producing hydrocarbons or carbon hydroxides from coal. Example 19: Alkyl aromatic hydrocarbon dehydration reaction

作为示例，甲苯蒸汽通入反应器。在 350°C 以上即见气体猛烈膨胀，且反应产物使高锰酸钾水溶液 (少于 1分钟)褪色和产生沉淀。作为对比，甲苯蒸汽通入一未装有催化剂的反应器，在同样条件下，反应产物在更长的通气时间 (约大于 5 分钟)仍然不能使使高锰酸钾水溶液褪色和产生沉淀 (实验发现，甲苯与高锰酸钾水溶液的混合物，经长时间后就会产生同样的褪色和沉淀效果)。甲苯因此在有催化剂的反应器中发生了如下的反应： As an example, toluene vapor is passed into the reactor. Above 350 ° C, violent gas expansion is seen, and the reaction product discolors the potassium permanganate aqueous solution (less than 1 minute) and precipitates. For comparison, toluene vapor was passed into a reactor without catalyst. Under the same conditions, the reaction product could not discolor the potassium permanganate aqueous solution and cause precipitation during a longer aeration time (about more than 5 minutes). It was found that a mixture of toluene and an aqueous potassium permanganate solution would produce the same discoloration and precipitation effect after a long time). Toluene therefore undergoes the following reaction in a catalyst reactor:

C₆H₅CH₃ C₆H₆+C₂H₄ (42) C ₆ H ₅ CH ₃ C ₆ H ₆ + C ₂ H ₄ (42)

或者由甲苯转化有苯、二甲苯，而二甲苯转化为乙苯，进一步地乙苯脱氢而产生苯乙烯，因为，苯乙烯可以快速地使高锰酸钾水溶液变色和产生沉淀。 Alternatively, toluene is converted into benzene and xylene, and xylene is converted into ethylbenzene, and further ethylbenzene is dehydrogenated to produce styrene, because styrene can rapidly discolor and precipitate potassium permanganate aqueous solution.

类似地其它含垸基芳香烃也应可以发生脱垸基的反应。实施例 20 : 醇与氨的反应 Similarly, other fluorenyl-containing aromatic hydrocarbons should be able to undergo dehydration reactions. Example 20: Reaction of alcohol with ammonia

作为示例，甲醇与氨同时通入反应器，当反应温度大于 300°C时，由在无水甲苯溶液中出口反应物与苦味酸作用生成黄色的苦味酸三甲胺盐而判定，（《化学试剂配制手册》，楼书聪编著，江苏科学技术出版社， 1993，第 639页)有三甲胺的产生。说明发生了下列系列反应： As an example, methanol and ammonia are introduced into the reactor at the same time. When the reaction temperature is greater than 300 ° C, it is determined by the reaction of the outlet reactants in anhydrous toluene solution with picric acid to generate yellow picric acid trimethylamine salt. (《Chemical Reagents Formulation Manual, edited by Lou Shucong, Jiangsu Science and Technology Press, 1993, p. 639) trimethylamine production. The following series of reactions have occurred:

CH₃OH+NH₃ → CH₃NH₂+¾O (43) CH ₃ OH + NH ₃ → CH ₃ NH ₂ + ¾O (43)

CH3OH+NH3 → (CH₃)₂NH+H₂O (44) CH3OH + NH3 → (CH ₃ ) ₂ NH + H ₂ O (44)

CH3OH+NH3 → (CH₃)₃N+H₂O (45) CH3OH + NH3 → (CH ₃ ) ₃ N + H ₂ O (45)

三种甲胺的分布应与具体的反应温度有关。其它醇类化合物与氨也应可以进行上述类似的反应。实施例 21 : 二氧化碳，氢气与氨及碳酸氢氨与氢气的反应当二氧化碳，氢气与氨同时通入反应器，或加热分解碳酸氢氨得到的气体与氢气同时通人反应器，在温度大于 520°C 时，即测得明显有氢氰酸的生成 (二氧化碳的转化率大于 15%)。该反应应是以下两步反应： The distribution of the three methylamines should be related to the specific reaction temperature. Other alcohol compounds and ammonia should be able to perform similar reactions as described above. Example 21: Reaction of carbon dioxide, hydrogen and ammonia and ammonia bicarbonate and hydrogen. When carbon dioxide, hydrogen and ammonia pass into the reactor at the same time, or gas obtained by heating and decomposing ammonia bicarbonate passes into the reactor at the same time, at a temperature greater than 520 At ° C, the formation of hydrocyanic acid is clearly measured (the conversion rate of carbon dioxide is greater than 15%). The reaction should be the following two-step reaction:

CO₂+H₂ -→> H₂O+CO (46) CO ₂ + H _2- →> H ₂ O + CO (46)

CO+NH₃ → HCN+H2O (47) CO + NH ₃ → HCN + H2O (47)

也许低温高压时也有甲酰胺的生成。上述反应说明二氧化碳与氢气的混合气体可以在此催化剂的作用下代替一氧化碳的使用。实施例 22 : 汽油的催化脱硫处理 Perhaps formamide is also formed at low temperature and pressure. The above reaction shows that a mixed gas of carbon dioxide and hydrogen can be used instead of carbon monoxide under the action of this catalyst. Example 22: Catalytic desulfurization of gasoline

本实施例的目的是为了将有机硫化物转化为易于脱除的无机硫化物 (如硫化氢)，以除去或减少燃油中的含硫量，及不饱和化合物的含量，同时能增加燃油的含氧量，实现改善燃油的燃烧性能和质量，减少其尾气对空气的污染。其中反应物汽油为市售的 90#汽油，其它如氢气、一氧化碳与水的混合物及水。 The purpose of this embodiment is to convert organic sulfides into inorganic sulfides (such as hydrogen sulfide) that can be easily removed, in order to remove or reduce the sulfur content in the fuel and the content of unsaturated compounds, and at the same time increase the fuel content The amount of oxygen can improve the combustion performance and quality of fuel, and reduce the pollution of air by its exhaust gas. The reactant gasoline is commercially available 90 # gasoline, and others such as hydrogen, a mixture of carbon monoxide and water, and water.

当仅有汽油进入反应器时，即使在温度达 650°C用乙酸铅试纸也未测出有硫化氢的产生。 When only gasoline entered the reactor, no hydrogen sulfide was detected even with lead acetate paper at temperatures up to 650 ° C.

当氢气进入汽油并携带汽油进人反应器后，在大于 200°C 时，用醋酸铅试纸测出有硫化氢的初步生成，随温度增加 (最高反应温度达 500°C)试纸颜色变为深亮黑色，说明硫化氢的含量得到增加。该反应为加氢脱硫的反应： After the hydrogen enters the gasoline and carries the gasoline into the reactor, the initial generation of hydrogen sulfide is detected with lead acetate test paper at a temperature greater than 200 ° C. The color of the test paper becomes darker as the temperature increases (the maximum reaction temperature reaches 500 ° C). Black indicates that the hydrogen sulfide content has increased. This reaction is a hydrodesulfurization reaction:

H₂+CnHmS → H₂S+CnHm， (48) H ₂ + CnHmS → H ₂ S + CnHm, (48)

及同时有不饱和化合物的加氢反应. And at the same time there are hydrogenation reactions of unsaturated compounds.

当一氧化碳分别通人热水及汽油后进入反应器，实验测出与上述类似的结果，说明有下述的反应： When carbon monoxide was passed into hot water and gasoline, and entered the reactor, the results similar to the above were measured experimentally, indicating the following reactions:

CO+H₂O → CO+H2 (49) CO + H ₂ O → CO + H2 (49)

H₂+CnHmS → H₂S+CnHm' (48) H ₂ + CnHmS → H ₂ S + CnHm '(48)

或同时有水与碳氢化合物或与一些含硫化合物的直接反应： Or there is a direct reaction of water with hydrocarbons or some sulfur compounds:

H₂O+CnHm → H₂+CO₂ (50) H ₂ O + CnHm → H ₂ + CO ₂ (50)

H₂0+CnHmS → H₂S+CnHm，O(醇或酮）（51) H ₂ 0 + CnHmS → H ₂ S + CnHm, O (alcohol or ketone) (51)

当只加热沸腾的水汽与加热蒸发的汽油进入反应器后，在温度大于 300°C 时，开始测出有硫化氢的生成，其含量随温度增加 (最高实验温度达 700°C)而迅速增加，说明有含硫化合物的水解反应： H₂O+CnHmS → H₂S+CnHm，O (醇或酮) (51) When only boiling water vapor and heated vaporized gasoline enter the reactor, when the temperature is greater than 300 ° C, the formation of hydrogen sulfide is measured, and its content increases rapidly with increasing temperature (the maximum experimental temperature reaches 700 ° C). , It shows that there are hydrolysis reactions of sulfur compounds: H ₂ O + CnHmS → H ₂ S + CnHm, O (alcohol or ketone) (51)

H₂O+CnHm → H₂+CO₂ (50)H ₂ O + CnHm → H ₂ + CO ₂ (50)

为了减少水与碳氢化合物生成氢气的反应，反应温度应尽可能的低. 实施例 23 : 复合催化材料与水及溶于水中氮的相互作用当复合催化材料在室温下置人水中时，通常由几分钟至数小时即可测得氨的形成；而当由氮气携带水份通过被加热的复合材料 (温度大于 100°C时)，可以立刻测得氨的形成。这是因为复合催化材料中所含的金属与水反应产生氢原子或氯分子，同时水中所溶的氮或携带气中的氮被复合催化材料所激活，从而它们进行反应生成氨。 In order to reduce the reaction between water and hydrocarbons to generate hydrogen, the reaction temperature should be as low as possible. Example 23: Interaction of composite catalytic materials with water and water-soluble nitrogen When the composite catalytic materials are placed in water at room temperature, usually The formation of ammonia can be measured from a few minutes to several hours; and when the moisture is carried by the nitrogen through the heated composite material (temperature greater than 100 ° C), the formation of ammonia can be measured immediately. This is because the metal contained in the composite catalytic material reacts with water to generate hydrogen atoms or chlorine molecules. At the same time, the nitrogen dissolved in the water or the nitrogen in the carrier gas is activated by the composite catalytic material, so that they react to generate ammonia.

上述情况氢由金属与水的化学反应而产生。类似的氢也可以通过电解水或电解其它溶解于适当电解液中的含氢化合物的方法而产生。实验中复合催化材料作为阴极，碳棒或铁片作为阳极，少量 NaOH作为电解质时，在 20伏直流电压， 0.5安培电流的情况下， 8小时后即可测得氨的生成。如把电极反向，即使 24小时后也测不出氨的生成。说明氨的形成是由于来自电解水产生的氢，该氢在复合催化材料表面与吸附的氮气反应而实现的。根据热力学原理，增加氮气的压力或分压将会增加氨的产率。由于氨水具有清洁的功能，所以上述电解方法可以作为一种工业或民用清洁物品的方法。 In this case, hydrogen is generated by a chemical reaction between metal and water. Similar hydrogen can also be produced by electrolyzing water or electrolyzing other hydrogen-containing compounds dissolved in a suitable electrolyte. In the experiment, the composite catalytic material was used as the cathode, carbon rods or iron plates as the anode, and a small amount of NaOH as the electrolyte. At 20 volts DC voltage and 0.5 amp current, ammonia production was measured after 8 hours. If the electrode is reversed, no ammonia can be detected even after 24 hours. It shows that the formation of ammonia is due to the hydrogen generated from the electrolyzed water, which is achieved by the reaction of the adsorbed nitrogen with the surface of the composite catalytic material. According to thermodynamic principles, increasing the pressure or partial pressure of nitrogen will increase the ammonia yield. Since ammonia water has a cleaning function, the above-mentioned electrolytic method can be used as a method for industrial or civilian cleaning articles.

因为此复合催化材料对非金属化合物的催化吸附作用，在将其作为电解电极处理有机物时亦将起到催化作用。实施例 24 ·· 水与氮气的反应 Because this composite catalytic material catalyzes the adsorption of non-metal compounds, it will also play a catalytic role when it is used as an electrolytic electrode to treat organic matter. Example 24Reaction of water and nitrogen

当氮与水进入反应器在温度大于 720°C时，氨的生成即开始突然增加，表现为 pH值的突然增加 (从 8至 10)。说明氮与水热分解出的氢反应生成了氨，另一产物应为氧。实验中反应最高温度达到 850°C。由于此反应为一体积缩小的反应，因此加大反应压力将有利于反应的进行。这种由水直接作为氢源合成氨的方法与通常用煤与水反应经氮气加氢气的过程相比具有容易净化原料、设备操作简单的特点。实施例 25 : 水与碳氢或碳氢氧、氮、氯及硫化合物的反应作为范例， 30%甲醇与水的共沸物，正己垸与水或苯与水的混合物经电炉加热形成沸腾的混合气体后进入反应器。实验发现在大于 300°C时，甲醇与水反应生成二氧化碳及其它产物如氢气，而在 400°C以上时，正己垸及苯与水反应生成二氧化碳及其它产物如氢气等。 When nitrogen and water enter the reactor at a temperature greater than 720 ° C, ammonia production begins to increase suddenly, manifested as a sudden increase in pH (from 8 to 10). It shows that the reaction between nitrogen and hydrothermally decomposed hydrogen produces ammonia, and the other product should be oxygen. The maximum reaction temperature in the experiment reached 850 ° C. Since this reaction is a reaction with a reduced volume, increasing the reaction pressure will facilitate the progress of the reaction. This method of synthesizing ammonia from water directly as a hydrogen source has the characteristics of easy purification of raw materials and simple operation of the equipment compared with the process of generally reacting coal with water by adding nitrogen to hydrogen. Example 25: As an example, the reaction of water with hydrocarbons or hydrocarbons, nitrogen, chlorine, and sulfur compounds. An azeotrope of 30% methanol and water, and a mixture of n-hexane and water or benzene and water were added by an electric furnace. The heat forms a boiling mixed gas and enters the reactor. Experiments have found that at temperatures above 300 ° C, methanol reacts with water to produce carbon dioxide and other products such as hydrogen, while above 400 ° C, n-hexane and benzene react with water to generate carbon dioxide and other products such as hydrogen.

而甲苯及二甲苯与水的混合气体分别在 400 , 480^eC以上温度时，不仅有二氧化碳的生成还伴有酚类的生成 (由汞加浓硝酸及水所配制成的溶液的试纸显淡红色测出)，其反应为： When toluene and xylene mixed with water at temperatures above 400, 480 ^e C, respectively, not only the formation of carbon dioxide but also the generation of phenols (the test paper of a solution made of mercury and concentrated nitric acid and water is light Measured in red), the response is:

C₆H₅CH₃+H₂O → C₆H₅OH+CH₄ (53) C ₆ H ₅ CH ₃ + H ₂ O → C ₆ H ₅ OH + CH ₄ (53)

C₆H₄(CH3)₂+H₂O - CH₄+C₆H₄或 (CH₃)(OH)C₆H₄(OH)₂ (54) 苯与水的混合气体在 600°C以上温度时仍未测出有酚类的生成，但通入氮气时，在 580°C时即测出有酚类的生成。相信这是由于氮气与苯反应生成联苯及氨，再经联苯与水的反应而产生酚的过程。 C ₆ H ₄ (CH3) ₂ + H ₂ O-CH ₄ + C ₆ H ₄ or (CH ₃ ) (OH) C ₆ H ₄ (OH) ₂ (54) The gas mixture of benzene and water is above 600 ° C The formation of phenols was not detected at the temperature, but the formation of phenols was detected at 580 ° C when nitrogen was introduced. It is believed that this is due to the reaction between nitrogen and benzene to form biphenyl and ammonia, and then the reaction of biphenyl with water to produce phenol.

类似地测出乙腈与水在大于 160^QC时发生水解生成了氨及二氧化碳等。而硝基苯与水在 180°C以上时反应生成了酸性物质，其 pH值达 1，该产物应为亚硝酸或为氮氧化物的分解产物，相应另一产物为苯酚。可见上述反应提供了一种新的生产苯酚的方法。其它硝基芳香烃或多环经化合物应有类似的水解反应。 It was similarly measured that acetonitrile and water were hydrolyzed to produce ammonia and carbon dioxide when the temperature was greater than 160 ^Q C. When nitrobenzene reacts with water above 180 ° C, an acidic substance is formed. Its pH value is 1. The product should be nitrous acid or a decomposition product of nitrogen oxides. The other product is phenol. It can be seen that the above reaction provides a new method for producing phenol. Other nitroaromatics or polycyclic compounds should undergo similar hydrolysis.

当水与氯苯共同加热至沸腾而进人反应器，温度为 600°C , 即开始有 HC1 的生成，其产物 pH值为 1 , 另一产物应为苯酚。当同时通人空气时则在 500°C 时即有酸性物质的生成。而此时的反应过程可能为氯苯首先与氧反应生成了更易水解的含氯产物。 When water and chlorobenzene are heated together to boil and enter the reactor at a temperature of 600 ° C, HC1 begins to form, and the product has a pH value of 1 and the other product should be phenol. When the air is passed in at the same time, acidic substances are generated at 500 ° C. The reaction process at this time may be that chlorobenzene first reacts with oxygen to form a more easily hydrolyzed chlorine-containing product.

当水汽与二硫化碳气体同时进人反应器时，温度大于 250°C即开始测得有硫化氢的生成，说明其可以用水解转化为 H₂S，或 COS，依反应条件而定。类似地，其它有机硫化物也可以用催化水解方法进行有机硫的脱除，如上述示范例中所显示的，存在于汽油中的硫化物即可经水解脱除或部分脱除。实施例 26：催化脱水 When water vapor and carbon disulfide gas enter the reactor at the same time, the generation of hydrogen sulfide is measured when the temperature is higher than 250 ° C, which indicates that it can be converted into H ₂ S, or COS by hydrolysis, depending on the reaction conditions. Similarly, other organic sulfides can also be used to remove organic sulfur by catalytic hydrolysis. As shown in the above example, the sulfides present in gasoline can be removed by hydrolysis or partially. Example 26: Catalytic dehydration

作为示范，甲醇，乙醇，正丁醇用于加热经催化剂的脱水反应。在 350°C以上时均可见水汽的生成，反应产物可以很快使高锰酸钾及溴水溶液脱色。说明脱水反应产物中有醚或烯的生成。如由甲醇脱水生成甲醚或由甲醚进一步脱水生成乙烯，乙醇脱水生成乙烯或***，及正丁醇脱水生成正丁醚等。 As an example, methanol, ethanol, and n-butanol are used to heat the dehydration reaction through the catalyst. The formation of water vapor can be seen above 350 ° C, and the reaction products can quickly decolor potassium permanganate and bromine aqueous solution. This indicates that ether or ene was formed in the dehydration reaction product. For example, methanol is dehydrated to form methyl ether or methyl ether is further dehydrated to form ethylene, ethanol is dehydrated to form ethylene or ether, and n-butanol is dehydrated to form n-butyl ether.

其它可能的用途如氮气传感器或用于对氮气含量变化的测量的使用。这是由于有反应： N₂+H₂O+Al ΝΗ₃+Α1₂Ο₃ (55) Other possible uses are for example nitrogen sensors or for the measurement of changes in nitrogen content. This is due to the response: N ₂ + H ₂ O + Al ΝΗ ₃ + Α1 ₂ Ο ₃ (55)

NH₃+H₂O NH₄ ⁺+OH" (56) NH ₃ + H ₂ O NH ₄ ⁺ + OH "(56)

在给定水汽浓度下，通过测量电阻，尤其是表面电阻的变化，或表面 pH值的变化，以显示出所测气氛中的氮气含量。 At a given water vapor concentration, the nitrogen content in the measured atmosphere is displayed by measuring the resistance, especially the change in surface resistance, or the change in surface pH.

在燃料电池的应用方面，由于新催化材料所具有的广泛的耐毒性，因此该催化材料可以容易地用于燃料电池的催化电极，并且还可以进行在电池电极过程中的部分氧化功能，以同时实现发电和产生有用的化学产品的用途。 In the application of fuel cells, due to the extensive toxicity resistance of the new catalytic material, the catalytic material can be easily used for the catalytic electrode of a fuel cell, and can also perform a partial oxidation function in the process of the battery electrode to simultaneously Realize the use of power generation and production of useful chemical products.

虽然本文对实施例或最优方案进行了描述，但不排除使用中可以进行改动、增加或减少一些细节或使用方法作些变动，这都不致偏离本发明权利要求所定义的发明范围和精祌实质。如在本文所给出的催化剂组成的基础上，在不影响催化效应的前提下减少一些物质或添加已知催化功能的成份以改进或加强催化剂的性能 (如活性、选择性)，或起到互相协同的作用。即用已知功能的催化材料与本文中的复合材料作进一步的复合以实现多功能催化，如与能使烃类和氨脱氢缩合为腈的催化剂 Cr₂O₃ , Fe₂O₃ , ΖηΟ (《有机化工原料大全》，魏文德主编，化学工业出版社， 1990 , 第 1卷，第 116页）等复合，即在复合材料制造过程中用过量的 Cr₂O₃ , Fe₂O₃ , ZnO，同时控制烧结温度、时间以使铝与这些物质进行适当程度的反应，实现氮气、烃类和氨脱氢生成腈的反应。或者直接利用含有表面氧化铝膜的细粉与气相或液相反应物进行充分混合以实现快速反应，如用于煤浆的加氢液化。或如对反应的原料路径在原有的基础上进行类似的变形，如用一氧化碳加水代替氢气。 Although the embodiment or the optimal solution is described herein, it is not excluded that changes, additions or deletions of details or changes in the use method can be made in use, which will not deviate from the scope and spirit of the invention defined by the claims of the present invention. substance. Based on the composition of the catalyst given in this article, without affecting the catalytic effect, reduce some substances or add components with known catalytic functions to improve or enhance the performance of the catalyst (such as activity, selectivity), or play a role Synergistic effect. That is, the catalytic materials with known functions are further compounded with the composite materials herein to achieve multifunctional catalysis, such as the catalysts Cr ₂ O ₃ , Fe ₂ O ₃ , Zn, which can dehydrocondensate hydrocarbons and ammonia into nitriles. ("Encyclopedia of Organic Chemical Materials", edited by Wei Wende, Chemical Industry Press, 1990, Vol. 1, p. 116) and other composites, that is, excessive use of Cr ₂ O ₃ , Fe ₂ O ₃ , ZnO in the manufacturing process of composite materials At the same time, the sintering temperature and time are controlled so that aluminum and these materials can react to an appropriate degree to achieve the reaction of dehydrogenation of nitrogen, hydrocarbons and ammonia to form nitrile. Alternatively, the fine powder containing the surface alumina film is directly mixed with the gas-phase or liquid-phase reactants to achieve rapid reaction, such as hydrogenation liquefaction of coal slurry. Or if the raw material path of the reaction is similarly modified on the original basis, such as carbon monoxide and water instead of hydrogen.

Claims

权利要求书 Request for Rights

I . 一种固体催化剂，其特征在于它是一种固体复合材料，包含附着在铝或铝合金上的氧化铝表面膜，或包含具有缺陷的岩盐结构的氧化铝。 I. A solid catalyst, characterized in that it is a solid composite material comprising an alumina surface film attached to aluminum or an aluminum alloy, or an alumina having a defective rock salt structure.

2. 根据权利要求 1所述的固体催化剂，其特征在于所述的氧化铝中还掺杂有选自元素周期表第 IA-VIA , IB-VIIB , VIII族或稀土元素中的一种或多种元素的原子。 2. The solid catalyst according to claim 1, wherein the alumina is further doped with one or more selected from the group consisting of Periodic Table IA-VIA, IB-VIIB, Group VIII or rare earth elements. Element of the atom.

3. 根据权利要求 1所述的固体催化剂，其特征在于所述的复合材料中还含有选自元素周期表第 IA-VIA , IB-VIIB , VHI族或稀土元素中的一种或多种元素。 3. The solid catalyst according to claim 1, characterized in that the composite material further contains one or more elements selected from the group consisting of elements IA-VIA, IB-VIIB, VHI group or rare earth elements of the periodic table of elements. .

4.根据权利要求 2所述的固体催化剂，其特征还在于所述的元素为钠，钾，镁，钙，钡，钇，钛，锆，钒，絡，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷，铋，硫或铈。 The solid catalyst according to claim 2, further characterized in that said elements are sodium, potassium, magnesium, calcium, barium, yttrium, titanium, zirconium, vanadium, complex, molybdenum, tungsten, manganese, iron, cobalt , Nickel, copper, zinc, boron, silicon, tin, phosphorus, bismuth, sulfur or cerium.

5.根据权利要求 3所述的固体催化剂，其特征还在于所述的元素为钠，钾，镁，钙，钡，钇，钛，锆，钒，铬，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷，铋，硫或铈。 The solid catalyst according to claim 3, wherein the elements are sodium, potassium, magnesium, calcium, barium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt , Nickel, copper, zinc, boron, silicon, tin, phosphorus, bismuth, sulfur or cerium.

6. 根据权利要求 3或 5所述的固体催化剂，其特征还在于所述元素以形成铝合金，铝的化合物，合金固溶体，氧化物和 /或单质的形态存在于复合材料中。 6. The solid catalyst according to claim 3 or 5, characterized in that the element exists in the composite material in the form of an aluminum alloy, an aluminum compound, an alloy solid solution, an oxide, and / or a simple substance.

7.根据权利要求 1-5任一权利要求所述的固体催化剂，其特征还在于所述的复合材料含有空隙。 The solid catalyst according to any one of claims 1 to 5, characterized in that the composite material contains voids.

8. 根据权利要求 6所述的固体催化剂，其特征还在于所述的复合材料含有空隙。 8. The solid catalyst according to claim 6, further characterized in that the composite material contains voids.

9. 根据权利要求 1所述的一种催化剂的制造方法，其特征在于该方法包括以下步骤： 9. The method for manufacturing a catalyst according to claim 1, wherein the method comprises the following steps:

Α、称取金属铝粉或其合金粉， Α, Weigh metal aluminum powder or its alloy powder,

C、对上述材料进行热处理或在含氧气氛下迸行热烧结。 C. Heat treatment of the above materials or thermal sintering in an oxygen-containing atmosphere.

10. 根据权利要求 9所述的一种催化剂的制造方法，其特征在于在步骤 Α之后还包括步骤： 10. The method for manufacturing a catalyst according to claim 9, further comprising steps after step A:

B、在压力下将所述的金属铝粉或其合金粉压縮成形。 B. Compress the metal aluminum powder or its alloy powder under pressure.

I I. 根据权利要求 10所述的一种催化剂的制造方法，其特征在于在步骤 C 之后还包括步骤： I I. A method for manufacturing a catalyst according to claim 10, further comprising steps after step C:

12. 根据权利要求 11所述的一种催化剂的制造方法，其特征还在于所述步骤 D可以在步骤 A或步骤 B之后进行。 12. The method for manufacturing a catalyst according to claim 11, further comprising: D can be performed after step A or step B.

13. 根据权利要求 9-12所述的一种催化剂的制造方法，其特征还在于步骤 C 中所述热处理或热烧结温度范围为常温- 1300 'C 。 13. The method for manufacturing a catalyst according to claims 9-12, further characterized in that the temperature range of the heat treatment or thermal sintering in step C is normal temperature-1300'C.

14. 根据权利要求 9-12所述的一种催化剂的制造方法，其特征在于其中所述的金属铝粉或其合金粉中进一步加入选自元素周期表第 IA-VIA , IB-VIIB , 14. A method for manufacturing a catalyst according to claims 9-12, characterized in that the metal aluminum powder or its alloy powder is further added to be selected from the group consisting of Periodic Table of the Elements IA-VIA, IB-VIIB,

VIII族或稀土元素中的一种或多种元素所组成的一种或多种物质粉末，并进行均匀混合。 Powder of one or more substances composed of one or more elements of Group VIII or rare earth elements, and uniformly mixed.

15. 根据权利要求 14所述的一种催化剂的制造方法，其特征还在于其中所述的元素为钠，钾，镁，钙，钡，钇，钛，锆，钒，铬，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷，铋，硫或铈。 15. The method for manufacturing a catalyst according to claim 14, further characterized in that said elements are sodium, potassium, magnesium, calcium, barium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, Manganese, iron, cobalt, nickel, copper, zinc, boron, silicon, tin, phosphorus, bismuth, sulfur or cerium.

16. 根据权利要求 13所述的一种催化剂的制造方法，其特征还在于其中所述的金属铝粉或其合金粉中进一步加人选自元素周期表第 IA-VIA , IB-VIIB , VIII族或稀土元素中的一种或多种元素所组成的一种或多种物质粉末，并进行均匀混合。 16. The method for manufacturing a catalyst according to claim 13, further characterized in that said metal aluminum powder or its alloy powder is further selected from the group consisting of Periodic Table of Elements IA-VIA, IB-VIIB, VIII Powder of one or more substances composed of one or more elements of the group or rare earth elements, and uniformly mixed.

17. 根据权利要求 16所述的一种催化剂的制造方法，其特征还在于其中所述的元素为钠，钾，镁，钙，钡，钇，钛，锆，钒，铬，钼，钨，锰，铁，钴，镍，铜，锌，硼，硅，锡，磷，铋，硫或铈。 17. The method for manufacturing a catalyst according to claim 16, further characterized in that said elements are sodium, potassium, magnesium, calcium, barium, yttrium, titanium, zirconium, vanadium, chromium, molybdenum, tungsten, Manganese, iron, cobalt, nickel, copper, zinc, boron, silicon, tin, phosphorus, bismuth, sulfur or cerium.

18. 根据权利要求 17所述的一种催化剂的制造方法，其特征在于它还包括步骤： 18. The method for manufacturing a catalyst according to claim 17, further comprising the steps of:

E、将所述经热处理或热烧结的催化剂材料切割或破碎成各种尺寸和形状。 E. Cutting or crushing the heat-treated or hot-sintered catalyst material into various sizes and shapes.

19. 根据权利要求 1-8任一权利要求所述的一种催化剂的应用，其特征在于它被用于制备氨，胺，苯，氢气，氮气，一氧化氮，二氧化碳，三氧化硫，氢腈酸，腈类，碳氢化合物，碳氢氧化合物，含氮化合物，含硫化合物或含氯化合物。 19. The use of a catalyst according to any one of claims 1-8, characterized in that it is used to prepare ammonia, amine, benzene, hydrogen, nitrogen, nitrogen monoxide, carbon dioxide, sulfur trioxide, hydrogen Nitric acids, nitriles, hydrocarbons, carbon hydroxides, nitrogen compounds, sulfur compounds or chlorine compounds.

20 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，所述方法包括下面几个步骤： 20. A method for applying a catalyst according to any one of claims 1-8, the method comprising the following steps:

A、把所述的复合材料放入一容器内， A. Put the composite material into a container,

B、加热所述的复合材料， B. heating said composite material,

C、通人反应气体或液体以实现催化反应， C. Passing in a reaction gas or liquid to achieve a catalytic reaction,

D、收集和分离反应产物，循环未完全反应的反应物及中间反应物。 21 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有氮气及氢气的合成氨反应，且所说催化反应的产物之一为氨。 D. Collect and separate reaction products, and circulate incompletely reacted reactants and intermediate reactants. 21. The method for applying a catalyst according to claim 1, wherein the reaction is a synthetic ammonia reaction containing nitrogen and hydrogen, and one of the products of the catalytic reaction is ammonia.

22 . 根据权利要求 1 -8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有氨的氨分解反应，且所说催化反应产物之一为氢气。 22. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction is an ammonia decomposition reaction containing ammonia, and one of the products of the catalytic reaction is hydrogen.

23 . 根据权利要求 1 -8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体含有氮气及二氧化氮，且所说催化反应产物之一为一氧化氮。 23. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction gas contains nitrogen and nitrogen dioxide, and one of the products of the catalytic reaction is nitric oxide.

24 . 根据权利要求 1 -8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有氮气及碳氢化合物或碳氢氧化合物、或含氮碳氢化合物或含氮碳氢氧化合物、或含硫碳氢化合物或含硫碳氢氧化合物、或含氯碳氢化合物或含氯碳氢氧化合物的氮气氧化反应，且所说催化反应产物之一为氨。 24. The method for applying a catalyst according to any one of claims 1 to 8, characterized in that the reaction comprises nitrogen and a hydrocarbon or a carbon hydroxide, or a nitrogen-containing hydrocarbon or a nitrogen-containing compound. Nitrogen oxidation reactions of carbon hydroxides, or sulfur-containing hydrocarbons or sulfur-containing carbon hydroxides, or chloro-hydrocarbons or chloro-carbon hydroxides, and one of the catalytic reaction products is ammonia.

25 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有氢气及碳氢或碳氢氧、或含氮碳氢或含氮碳氯氧化合物、或含硫碳氢或含硫碳氢氧化合物、或含氯碳氢或含氯碳氢氧化合物的加氢反应，且所述催化反应产物之一为新的碳氢或碳氢氧化合物、或含氮、或含硫、或含氯的化合物。 25. The method for applying a catalyst according to any one of claims 1-8, characterized in that the reaction comprises hydrogen and hydrocarbon or hydrocarbon or nitrogen-containing hydrocarbon or nitrogen-containing carbon-oxygen A hydrogenation reaction of a compound, or a sulfur-containing hydrocarbon or a sulfur-containing carbon hydroxide, or a chlorine-containing hydrocarbon or a chlorine-containing carbon hydroxide, and one of the products of the catalytic reaction is a new hydrocarbon or a carbon hydroxide , Or nitrogen, or sulfur, or chlorine compounds.

26 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有空气 (氧气)及碳氢或碳氢氧化合物的空气 (氧气)氧化反应，且所述催化反应产物之一为新的碳氢氧化合物。 26. A method for applying a catalyst according to any one of claims 1-8, characterized in that the reaction is an air (oxygen) oxidation reaction containing air (oxygen) and a hydrocarbon or a carbon hydroxide, And one of the catalytic reaction products is a new carbon hydroxide.

27 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为氨、空气 (氧气)及碳氢或碳氢氧化合物的氨空气氧化反应，且所说催化反应产物之一为氢氰酸或腈类。 27. The method for applying a catalyst according to any one of claims 1-8, wherein the reaction is an ammonia air oxidation reaction of ammonia, air (oxygen), and a hydrocarbon or a carbon hydroxide, and One of the catalytic reaction products is hydrocyanic acid or nitriles.

28 . 根据权利要求 1 -8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为盐酸、空气 (氧气)及碳氢化合物的氧氯化反应，且所说催化反应产物之一为含氯碳氢化合物。 28. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction is an oxychlorination reaction of hydrochloric acid, air (oxygen), and a hydrocarbon, and the catalytic reaction One of the products is a chlorohydrocarbon.

29 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为空气 (氧气)及硫化氢或二氧化硫的氧化反应，且所述催化反应产物之一为三氧化硫。 29. The method for applying a catalyst according to claim 1, wherein the reaction is an oxidation reaction of air (oxygen) and hydrogen sulfide or sulfur dioxide, and one of the products of the catalytic reaction For sulfur trioxide.

30 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含垸基的芳香族化合物的脱烷基的反应，特别是甲苯的脱烷基反应，且所述催化反应产物之一为苯。 30. The method for applying a catalyst according to claim 1, wherein the reaction is a dealkylation reaction of an aromatic compound containing a fluorenyl group, in particular a dealkylation of toluene. Reaction, and one of the catalytic reaction products is benzene.

31 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有水及碳氢或碳氢氧化合物、或含氮碳氢或含氣碳氢氧化合物、或含硫碳氢或含硫碳氢氧化合物、或含氯碳氢或含氯碳氢氧化合物的水解反应，且所述催化反应产物之一为氢气或新的碳氢或碳氢氧化合物、或含氮、或含硫、或含氯的化合物。 31. The method for applying a catalyst according to any one of claims 1 to 8, characterized in that the reaction comprises water and a hydrocarbon or a carbon hydroxide, or a nitrogen-containing hydrocarbon or a gas-containing hydrocarbon Hydrolysis reaction of oxygen compounds, or sulfur-containing hydrocarbons or sulfur-containing carbon hydroxides, or chlorine-containing hydrocarbons or chlorine-containing carbon hydroxides, and one of the catalytic reaction products is hydrogen or new hydrocarbons or hydrocarbons Oxygen compounds, or containing nitrogen, or containing Sulfur, or chlorine-containing compounds.

32 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体或液体含有水及氮气，且所述催化反应产物之一为氨。 32. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction gas or liquid contains water and nitrogen, and one of the catalytic reaction products is ammonia.

33 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含氧碳氢化合物的脱水反应，且所述催化反应产物之一为水。 33. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction is a dehydration reaction of an oxygen-containing hydrocarbon, and one of the products of the catalytic reaction is water.

34.根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为醇与氨的脱水反应，且所述催化反应产物之一为胺。 34. The method for applying a catalyst according to any one of claims 1 to 8, characterized in that the reaction is a dehydration reaction of an alcohol and ammonia, and one of the products of the catalytic reaction is an amine.

35 . 根据权利要求 1 -8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体或液体含有一氧化碳及含氧碳氢化合物，且所述催化反应产物之一为二氧化碳。 35. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction gas or liquid contains carbon monoxide and oxygen-containing hydrocarbons, and one of the catalytic reaction products is carbon dioxide .

36 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体或液体含有一氧化碳、水及硝基化合物，且所述催化反应产物之一为胺。 36. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction gas or liquid contains carbon monoxide, water, and a nitro compound, and one of the catalytic reaction products is an amine .

37 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体或液体含有二氧化碳、氢气及氨，且所述催化反应产物之一为氢氰酸。 37. The method for applying a catalyst according to any one of claims 1-8, wherein the reaction gas or liquid contains carbon dioxide, hydrogen, and ammonia, and one of the catalytic reaction products is hydrocyanic acid .

38 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为含有一氧化碳及氢气的合成反应，且所说催化反应产物之一为碳氢或碳氢氧化合物。 38. The method for applying a catalyst according to any one of claims 1-8, wherein the reaction is a synthesis reaction containing carbon monoxide and hydrogen, and one of the products of the catalytic reaction is hydrocarbon or carbon Hydroxide.

39 . 根据权利要求 1 -8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体或液体含有一氧化碳及氨，且所述催化反应产物之一为氢氰酸。 39. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction gas or liquid contains carbon monoxide and ammonia, and one of the catalytic reaction products is hydrocyanic acid.

40 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应气体或液体含有一氧化碳及水，且所述催化反应产物之一为二氧化碳。 40. The method for applying a catalyst according to any one of claims 1 to 8, wherein the reaction gas or liquid contains carbon monoxide and water, and one of the catalytic reaction products is carbon dioxide.

41 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为氮氧化物及一氧化碳或氨的还原脱硝反应，且所说催化反应产物之一为氮气。 41. The method for applying a catalyst according to any one of claims 1-8, wherein the reaction is a reduction and denitration reaction of nitrogen oxides and carbon monoxide or ammonia, and one of the products of the catalytic reaction is Nitrogen.

42 . 根据权利要求 1-8任一权利要求所述的一种催化剂的应用方法，其特征在于所述反应为氮气与来自含氢离子或可分解出氢的无机或有机化合物的电解、电离、光分解、热分解或化学反应而产生的自由氢的氨合成反应，且所述催化反应产物之一为氨。 42. The method for applying a catalyst according to any one of claims 1 to 8, characterized in that the reaction is the electrolysis, ionization, Ammonia synthesis reaction of free hydrogen generated by photodecomposition, thermal decomposition or chemical reaction, and one of the catalytic reaction products is ammonia.