WO2000025912A1 - Catalyseur solide, son procede de preparation et son utilisation - Google Patents

Catalyseur solide, son procede de preparation et son utilisation Download PDF

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Publication number
WO2000025912A1
WO2000025912A1 PCT/CN1999/000177 CN9900177W WO0025912A1 WO 2000025912 A1 WO2000025912 A1 WO 2000025912A1 CN 9900177 W CN9900177 W CN 9900177W WO 0025912 A1 WO0025912 A1 WO 0025912A1
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reaction
catalyst according
nitrogen
ammonia
catalytic
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PCT/CN1999/000177
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English (en)
Chinese (zh)
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Caidong Qin
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Caidong Qin
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Priority to AU64594/99A priority Critical patent/AU6459499A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the method for manufacturing the catalyst of the present invention includes the following steps:
  • Step A can also include steps:
  • Step C can also include steps:
  • step C The material obtained in step C is further subjected to chemical or anodizing treatment in an oxidizing chemical solution.
  • step D may be after step C, or after step A or B.
  • 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.
  • 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.
  • the heat-treated or heat-sintered catalyst material of the present invention can be cut or broken into various sizes and shapes as required.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a compound composed of some non-metal elements especially a compound formed between carbon, hydrogen, oxygen, nitrogen, sulfur, and chlorine
  • 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.
  • 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.
  • 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.
  • 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.
  • aluminum alloy refers generally to alloys (including alloys formed with semimetals) containing aluminum.
  • alumina film and “bulky alumina” refer to the difference in crystal structure, not just the difference in morphology.
  • 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.
  • 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.
  • 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
  • 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.
  • 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) ).
  • 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.
  • 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).
  • 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.
  • 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.
  • the composite material 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the alumina surface film with this special structure is only found on the surface of metal aluminum (inorganic chemistry series, Vietnamese 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.
  • 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.
  • 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.
  • 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.)
  • 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.
  • 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. .
  • 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.
  • 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, Vietnamese Heiwen, Tangalo). (Eds., Science Press, 1998, Vol. 2, p.
  • 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. .
  • 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.
  • 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).
  • 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.
  • 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
  • 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.
  • the experiment 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.
  • this alumina surface film 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.
  • 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:
  • 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;
  • HN H bridged end structure
  • N 2 H 2 Trans. 1981, p. 70 This step is an endothermic process.
  • 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) .
  • 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.
  • 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.
  • 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.
  • the product hydrazine (N 2 ) will be obtained.
  • reaction process of nitrogen plus hydrogen should be divided into the following reversible and approximately irreversible parts:
  • 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.
  • 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.
  • the catalyst can achieve a catalytic reaction of partial oxidation of oxygen.
  • 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.
  • 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.
  • Catalyst composites made of aluminum and calcium oxide help avoid experiments
  • the catalytic properties found in this are confused with the role of known catalytic components.
  • nickel 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.
  • 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.
  • the experimental parameters used in the catalytic reaction are for reference only and are not a limitation on future use.
  • 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.
  • 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.
  • the gas also plays the role of carrying gas at the same time; or the liquid is directly flowed into the reaction
  • 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.
  • 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.
  • 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.
  • 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.
  • 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:
  • hydrazine 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.
  • One example is the reaction between nitrogen and formamidine (1:10 volume ratio).
  • 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:
  • 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.
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. .
  • 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.
  • nitrogen oxidative dehydrogenation does not have the problem of deep oxidation to generate water and carbon dioxide.
  • 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.
  • 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.
  • 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:
  • benzene, toluene, xylene carbon-carbon double bond hydrogenation reaction
  • acetonitrile nitrobenzene
  • nitroformamidine nitrile and nitro compound hydrogenation
  • Reaction of hydrogen to amine and carbon disulfide (hydrodesulfurization reaction), and chlorobenzene, carbon tetrachloride (hydrodechlorination reaction), carboxylic acid hydrogenation and acetone ammonia hydrogenation reaction.
  • 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:
  • 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.
  • 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.
  • acetic acid was used in the hydrogenation test.
  • 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:
  • acetone was tested with ammonia and hydrogen.
  • 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).
  • 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.
  • acetylene, ethylene, or propylene, propylene is used to realize the cycle of nitrogen oxidative dehydrogenation and hydrogenation.
  • 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.
  • 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).
  • oxygen oxygen
  • 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.
  • 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);
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the starting temperatures of benzene, toluene, xylene and styrene to produce acidic reaction products are 450, 380,
  • 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.
  • the reaction temperature increases, it eventually becomes a combustion reaction of carbon dioxide and water.
  • 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
  • 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.
  • advanced nitriles should be formed, such as acetonitrile, propionitrile, acrylonitrile, butyronitrile, and aromatic nitrile. .
  • 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.
  • concentrated hydrochloric acid content 36%) is carried into the reactor by the passing air.
  • 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).
  • n-heptane 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.
  • the catalyst should also be able to achieve the industrially significant reaction of oxychloroethylene to produce vinyl chloride.
  • 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.
  • 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 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:
  • 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.
  • 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
  • Nitrogen dioxide was obtained in the experiment as described above with copper and concentrated nitric acid.
  • 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)
  • reaction temperature is greater than 200 ° C, the generation of carbon dioxide is measured.
  • the reaction is:
  • 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.
  • 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.
  • 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
  • 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:
  • toluene is converted into benzene and xylene
  • xylene is converted into ethylbenzene
  • further ethylbenzene is dehydrogenated to produce styrene, because styrene can rapidly discolor and precipitate potassium permanganate aqueous solution.
  • methanol and ammonia are introduced into the reactor at the same time.
  • 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:
  • 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:
  • 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.
  • Example 23 Interaction of composite catalytic materials with water and water-soluble nitrogen
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 24 Reaction of water and nitrogen
  • 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.
  • methanol is dehydrated to form methyl ether or methyl ether is further dehydrated to form ethylene
  • ethanol is dehydrated to form ethylene or ether
  • n-butanol is dehydrated to form n-butyl ether.
  • 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.
  • 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.
  • 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.
  • multifunctional catalysis such as the catalysts Cr 2 O 3 , Fe 2 O 3 , Zn
  • Cr 2 O 3 , Fe 2 O 3 , Zn which can dehydrocondensate hydrocarbons and ammonia into nitriles.
  • 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.
  • 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.
  • the raw material path of the reaction is similarly modified on the original basis, such as carbon monoxide and water instead of hydrogen.

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Abstract

L'invention concerne un catalyseur solide, son procédé de préparation et son utilisation. Ce catalyseur est formé d'une matière composite solide renfermant un film d'oxyde d'aluminium recouvrant la surface de l'aluminium métal ou de l'alliage aluminium ou d'oxyde d'aluminium présentant une structure halite défectueuse. Ce catalyseur peut activer efficacement les composés contenant du carbone, hydrogène, oxygène, azote, soufre et chlore et peut être utilisé pour catalyser la réaction se produisant entre l'azote et l'hydrogène (la synthèse d'ammonium), la décomposition d'ammonium et la réaction entre un azote et des hydrocarbures (la déshydrogénation catalytique avec un azote en tant qu'oxydant), l'ammoxydation ou l'oxychloration. Il peut aussi trouver une application dans l'hydrogénation ou l'oxydation du composé organique, l'hydrolyse ou la déshydrations et la réaction électrolytique de la synthèse d'ammonium par des processus électrolytiques.
PCT/CN1999/000177 1998-11-04 1999-11-01 Catalyseur solide, son procede de preparation et son utilisation WO2000025912A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5295590A (en) * 1976-02-09 1977-08-11 Riken Keikinzoku Kogyo Kk Catalyst carriers and the manufacture
JPS5478391A (en) * 1977-12-06 1979-06-22 Riken Keikinzoku Kogyo Kk Catalyst and manufacture
US4681668A (en) * 1984-11-05 1987-07-21 Alcan International Limited Anodic aluminium oxide film and method of forming it
EP0284804A1 (fr) * 1987-03-16 1988-10-05 Emitec Gesellschaft für Emissionstechnologie mbH Procédé d'oxydation de la surface d'un support de catalyseur
EP0390321A1 (fr) * 1989-03-14 1990-10-03 Corning Incorporated Structure métallique frittée poreux comprenant une couche à durcissement oxydant
US5294586A (en) * 1992-06-25 1994-03-15 General Motors Corporation Hydrogen-water vapor pretreatment of Fe-Cr-Al alloys

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5295590A (en) * 1976-02-09 1977-08-11 Riken Keikinzoku Kogyo Kk Catalyst carriers and the manufacture
JPS5478391A (en) * 1977-12-06 1979-06-22 Riken Keikinzoku Kogyo Kk Catalyst and manufacture
US4681668A (en) * 1984-11-05 1987-07-21 Alcan International Limited Anodic aluminium oxide film and method of forming it
EP0284804A1 (fr) * 1987-03-16 1988-10-05 Emitec Gesellschaft für Emissionstechnologie mbH Procédé d'oxydation de la surface d'un support de catalyseur
EP0390321A1 (fr) * 1989-03-14 1990-10-03 Corning Incorporated Structure métallique frittée poreux comprenant une couche à durcissement oxydant
US5294586A (en) * 1992-06-25 1994-03-15 General Motors Corporation Hydrogen-water vapor pretreatment of Fe-Cr-Al alloys

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