Liquid phase ammonia related catalyst and application thereof

Abstract

The invention provides a liquid-phase ammonia-related catalyst and application thereof. The liquid-phase ammonia-related catalyst is prepared by mutually dissolving at least two elements selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, gold, gallium, indium, tin, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, aluminum, sulfur, selenium and tellurium in a liquid state. Wherein the liquid-phase ammonia-related catalyst is a catalyst which is in a liquid state under reaction conditions and is related to ammonia reactions, and the ammonia reactions comprise an ammonia decomposition reaction, an ammonia synthesis reaction and an SCR denitration reaction; the problems that in the prior art, a catalyst for an ammonia chemical reaction is prone to inactivation, poor in stability, high in preparation cost, poor in catalytic effect and the like can be solved.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst design and application, and more specifically, to a liquid-phase ammonia-related catalyst and application thereof. Background Art

[0002] Ammonia is a key inorganic chemical product, with approximately 80% used in the production of chemical fertilizers and 20% as raw materials for other chemical products. Three chemical reactions involving ammonia are particularly important: ammonia synthesis, ammonia decomposition to produce hydrogen, and SCR-NH3 selective catalytic reduction (SCR) denitrification technology. Fertilizers made from synthetic ammonia can accelerate plant growth and increase yields, thereby improving crop production efficiency. Synthetic ammonia is widely used in the chemical industry, for example, in the manufacture of nitric acid, various nitrogen-containing inorganic salts and organic intermediates, cellulose, sulfonamides, polyurethanes, polyamide fibers, nitrile rubber, explosives, dyes, and other products. Furthermore, the production of synthetic ammonia from syngas produces a large number of byproducts, such as methanol and ethanol.

[0003] However, industrial ammonia synthesis currently still utilizes the Haber-Bosch (HB) process, which requires high temperature and high pressure (350-550°C, 10-30 MPa) and consumes 1%-2% of the global energy supply. It also emits approximately 500 million tons of carbon dioxide annually, accounting for approximately 1.8% of global CO2 emissions. Furthermore, BASF's century-old molten iron catalyst still dominates industrial production. While highly active, ruthenium catalysts are strongly inhibited by H2. Carbon-supported Ru catalysts undergo methanation under ammonia synthesis conditions, resulting in loss of the activated carbon support. Furthermore, Ru and Os are very expensive, and Ru / C catalysts offer limited energy savings. Therefore, the development of clean, efficient, and "green" ammonia synthesis catalytic systems is crucial. These include lowering reaction temperatures, increasing equilibrium ammonia conversion, improving reaction conditions, reducing power consumption, and improving ammonia production efficiency.

[0004] Hydrogen energy is an efficient and clean form of energy. However, its low bulk density and difficulty in liquefaction make its storage and transportation face a series of technical obstacles. Ammonia is an excellent chemical hydrogen storage medium with a high hydrogen content (17.75% by mass), easy liquefaction (0.8MPa, 298K), easy storage and transportation, and no harmful impurities such as COx. However, Ru-based catalysts for ammonia decomposition to produce hydrogen have advantages such as high activity and high stability at low temperatures, but they are expensive and have high usage costs. Non-precious metal catalysts such as Ni, Fe, and Co are low in cost, but have low activity and slow reaction rates. Under high temperature conditions (650-750°C), the catalysts are easily deactivated, and the process energy consumption is high. It is imperative to develop low-cost, highly active, and highly stable ammonia decomposition catalysts.

[0005] Nitrogen oxides (NO x) is a common air pollutant that poses a great threat to human health and the ecological environment. It mainly comes from coal-fired boilers and motor vehicle exhaust emissions. Selective catalytic reduction (SCR) technology is a technology that reduces NO x An effective way to remove pollutants is to catalyze the reaction of nitrogen oxides in flue gas with a reducing agent (NH3-SCR) to produce N2 and H2O, thereby reducing or eliminating nitrogen oxide pollution in the atmosphere. It produces no byproducts, does not cause secondary pollution, has a simple device structure, and offers high removal efficiencies (over 90%), reliable operation, and is easy to maintain. Several types of catalysts are available, including precious metals, molecular sieves, and metal oxides. Precious metals are relatively expensive, while molecular sieves have narrow pore sizes and high diffusion resistance. Vanadium-based metal oxide catalysts (such as V2O5-WO3 / TiO2) offer a wide variety of raw materials, simple preparation, and consistently achieve denitrification efficiencies exceeding 90%, making them widely used in flue gas denitrification for industrial boilers and kilns. However, the vanadium in vanadium-based catalysts is toxic; their low-temperature reactivity is low; and high-temperature applications in coal- and oil-fired applications face high dusty flue gas conditions, making them susceptible to clogging and coating, leading to catalyst failure. Furthermore, their water and sulfur resistance properties need improvement.

[0006] On the other hand, liquid catalysts are mostly used for homogeneous catalytic reactions. In most solid catalysts for heterogeneous catalysis, the atoms on the solid surface have a clear position, they vibrate with small amplitudes around them, the surface has periodicity, and the active sites caused by dissociative adsorption are few and fixed. When the surface is liquid, because the surface atoms are mobile and form many configurations with transient lifespans; in addition, liquid atoms have higher mobility and can undergo larger displacements to adapt to the bonding "needs" of dissociated fragments; therefore, liquid catalysts have more active sites, and unlike solid catalysts that are rapidly deactivated due to factors including carbon deposition (coking), liquids provide a constantly updated gas-liquid interface and an environment for continuous separation of by-products (such as solid carbon). However, liquid catalysts using the bubbling principle have a relatively small catalytic area (e.g., the size of bubbles is 0.1-1 cm, while solid catalysts can often achieve particles or micropores with a diameter of 10-100 nm). Conventional liquid catalysts are not very active and have a disadvantageous catalytic area, so they have not been widely used in industry. Moreover, the solvents of general liquid catalysts are mainly water, organic solvents, and ionic liquids, and the operating temperature is not high, making them inapplicable to the above-mentioned ammonia-related reactions. Therefore, there are few research reports on the use of liquid catalysts for the above-mentioned three ammonia-related reactions.

[0007] Therefore, developing a highly active heterogeneous liquid catalyst that can achieve the above-mentioned ammonia-related chemical reactions is a major challenge. Summary of the Invention

[0008] In view of the above problems, the purpose of the present invention is to provide a liquid-phase ammonia-related catalyst and its application to solve the problems of easy deactivation, poor stability, high preparation cost and poor catalytic effect of catalysts in the current existing technology for ammonia chemical reactions.

[0009] The present invention provides a liquid-phase ammonia-related catalyst, which is prepared by dissolving at least two elements selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, gold, gallium, indium, tin, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, aluminum, sulfur, selenium, and tellurium in each other in a liquid state; wherein the liquid-phase ammonia-related catalyst refers to a catalyst involving an ammonia reaction that is liquid under reaction conditions.

[0010] In addition, a preferred embodiment is that the content of each element accounts for 0.01-99.99at.% of the liquid-phase ammonia-related catalyst, where at. represents the atomic fraction; when the liquid-phase ammonia-related catalyst includes a transition metal element, the proportion of the transition metal element in the liquid-phase ammonia-related catalyst does not exceed 90at.%; wherein the transition metal element includes at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, and gold.

[0011] In addition, a preferred scheme is to select one or at least two elements from manganese, iron, and ruthenium as the first component; select one or at least two elements from gallium, indium, tin, lead, bismuth, lanthanum, cerium, and samarium as the second component; and dissolve the first component and the second component in each other in liquid state to form the liquid-phase ammonia-related catalyst.

[0012] In addition, a preferred scheme is to select one or at least two elements from manganese, iron, and ruthenium as the first component; select one or at least two elements from gallium, indium, tin, lead, bismuth, lanthanum, cerium, and samarium as the second component; select one or at least two elements from lithium, sodium, potassium, rubidium, cesium, francium, magnesium, and calcium as the third component; or, select one or at least two elements from lithium, sodium, potassium, rubidium, cesium, and francium as the third component; or, select one or at least two elements from magnesium and calcium as the third component; and dissolve the first component, the second component, and the third component in liquid state to form the liquid-phase ammonia-related catalyst.

[0013] In addition, a preferred embodiment is that the liquid-phase ammonia-related catalyst is a liquid in which all material components are mutually soluble, and is obtained by pre-dissolving at room temperature or pre-heating and melting; or, directly heating and melting to a liquid state under reaction conditions; or, mixing a source material containing the element selected as the liquid-phase ammonia-related catalyst with a carrier and a solvent of the catalyst to obtain a suspension; filtering and drying the suspension in sequence to obtain a catalyst precursor; calcining the precursor and performing a reduction reaction in a reducing gas atmosphere to obtain a carrier-supported liquid-phase ammonia-related catalyst, and the liquid-phase ammonia-related catalyst load is in a liquid state under reaction conditions.

[0014] In addition, a preferred embodiment is that the liquid-phase ammonia-related catalyst is a droplet-type catalyst when used; wherein the droplet diameter of the droplet-type catalyst is less than 0.1 mm; the preparation method of the droplet-type catalyst is: the liquid-phase ammonia-related catalyst is atomized into a droplet-type catalyst by any one of pressurization, dual-flow atomization, ultrasound, and centrifugation; or, the liquid-phase ammonia-related catalyst is made into an ultrafine powder by any one of rapid cooling after liquid atomization, electron beam rapid quenching, laser surface melting, and mechanical crushing, and the ultrafine powder is placed in a container and heated to form a droplet-type catalyst; or, the constituent substances of the liquid-phase ammonia-related catalyst are loaded on a carrier, and the constituent substances are melted on the carrier by heating and heating to form a droplet-type catalyst; or, the liquid-phase ammonia-related catalyst is heated to evaporate and then condensed to form droplet reflux to obtain a droplet-type catalyst.

[0015] The present invention provides an application of a liquid-phase ammonia-related catalyst, wherein the liquid-phase ammonia-related catalyst is applied to an ammonia decomposition reaction, an ammonia synthesis reaction, or an SCR denitration reaction.

[0016] In addition, a preferred embodiment is that the liquid-phase ammonia-related catalyst is applied to an ammonia decomposition reaction, comprising the following steps:

[0017] Under the condition of reaction temperature of 500-1500°C, the reaction raw material NH3 is introduced into the bottom of the container containing the liquid phase ammonia-related catalyst;

[0018] The NH3 bubbles float up and come into interfacial contact with the liquid-phase ammonia-related catalyst to generate a catalytic reaction to generate products H2 and N2;

[0019] The product H2, the product N2 and unreacted NH3 are separated.

[0020] In addition, a preferred embodiment is that the liquid-phase ammonia-related catalyst is applied to an ammonia decomposition reaction, comprising the following steps:

[0021] The reaction raw material NH3 is introduced into a container filled with droplets of the liquid-phase ammonia-related catalyst and allowed to remain there for a first preset time, so that the reactant comes into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst, a catalytic reaction occurs, and the product H2 and the product N2 are generated;

[0022] The product H2, the product N2 and the unreacted NH3 are separated, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from impurities for reuse.

[0023] In addition, a preferred solution is that the liquid-phase ammonia-related catalyst is applied to a synthetic ammonia reaction, comprising the following steps:

[0024] Under the conditions of a reaction temperature of 400-1000°C and a reaction pressure of 0.1-50 MPa, the mixed reaction gas obtained by mixing the reaction raw materials H2 and N2 is introduced into the bottom of the container containing the liquid phase ammonia-related catalyst;

[0025] The bubbles of the mixed reaction gas float up and come into interfacial contact with the liquid-phase ammonia-related catalyst, causing a catalytic reaction to generate product NH3;

[0026] The unreacted reaction raw material H2, the unreacted reaction raw material N2 and the product NH3 are separated.

[0027] In addition, a preferred solution is that the liquid-phase ammonia-related catalyst is applied to a synthetic ammonia reaction, comprising the following steps:

[0028] The reaction raw materials H2 and N2 are introduced into a container filled with droplets of the liquid-phase ammonia-related catalyst and allowed to remain there for a predetermined time, so that the reaction raw materials come into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst, a catalytic reaction occurs, and the product NH3 is generated;

[0029] The product NH3 and the unreacted reaction raw materials H2 and N2 are separated, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from impurities for reuse.

[0030] In addition, a preferred solution is that the liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps:

[0031] Under the condition of reaction temperature of 280-1200°C, the reaction raw materials NH3 and NO-containing reaction raw gas are introduced into the bottom of the container containing the liquid phase ammonia-related catalyst;

[0032] The bubbles of the reaction raw material NH3 and the reaction raw material gas containing NO float up and come into interfacial contact with the liquid phase ammonia-related catalyst, causing a catalytic reaction. The gaseous products and unreacted products float to the liquid surface and are then treated and discharged to complete the SCR denitration reaction.

[0033] In addition, a preferred solution is that the liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps:

[0034] Passing the reaction raw materials NH3 and the reaction raw material gas containing NO into a container filled with the droplets of the liquid-phase ammonia-related catalyst and holding them for a second preset time, so that the reaction raw materials come into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst and a catalytic reaction occurs;

[0035] The gaseous products and unreacted gaseous reaction raw materials generated in the catalytic reaction are discharged after treatment, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from impurities before being reused.

[0036] In addition, a preferred solution is that the liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps:

[0037] Spraying the reaction raw material NH3 and the droplets of the liquid-phase ammonia-related catalyst into the flue gas containing the NO reaction raw material gas, so that the reaction raw material NH3 and the flue gas containing the NO reaction raw material gas are in interfacial contact with the droplets of the liquid-phase ammonia-related catalyst to cause a catalytic reaction;

[0038] The gaseous products and unreacted gaseous reaction raw materials produced in the catalytic reaction are discharged after treatment, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from the impurities and unreacted solid reaction raw materials before being reused.

[0039] In addition, a preferred solution is to pre-load the material components of the liquid-phase ammonia-related catalyst on the surface of a solid support and introduce them into the reaction vessel in solid form. Under reaction conditions, the surface material components of the solid support are heated and melted into droplets, so that the gaseous reactants flow through the solid support and fully contact the droplets on the solid support.

[0040] The reaction vessel is a fluidized bed reactor, and the liquid-phase ammonia-related catalyst reacts with the gaseous reactants in the fluidized bed in the form of droplets; or

[0041] The reaction container is a fixed bed reactor, the catalyst supported on the surface of the solid carrier in the form of droplets is pre-filled in the fixed bed reactor, and the gaseous reactant flows through the fixed bed to undergo a catalytic reaction.

[0042] It can be seen from the above technical scheme that the liquid-phase ammonia-related catalyst and its application provided by the present invention greatly reduce the preparation cost of the catalyst by adopting cheap and resource-rich elements to replace precious metals, or adopting ordinary inorganic salts; and can be multi-combined as needed to play the synergistic catalytic role of multiple elements and components; it is prepared by dissolving the substances in the formula in liquid state, the preparation method is simple and the quality is uniform and controllable, and it is suitable for large-scale production; the liquid-phase ammonia-related catalyst provided by the present invention has high activity and efficiency, especially the efficiency of synthesizing ammonia is better than traditional molten iron catalysts and expensive ruthenium catalysts, and has high stability and is not easy to deactivate and poison; the catalyst can also adapt to harsh working conditions, especially for catalytic denitrification. Most of the existing denitrification uses low-temperature denitrification after dust removal. At this time, the Ru catalyst is expensive and not very active. The liquid-phase ammonia-related catalyst provided by the present invention can be directly sprayed into the flue gas with ammonia in the form of liquid droplets, or the flue gas can be bubbled from the bottom of the liquid-phase catalyst. During use, it can withstand high temperatures and high dust and ash without affecting the catalytic activity. It can also resist the poisoning of sulfur oxides, so it can be arranged in the high-temperature section before dust removal; the catalyst is easy to separate from the solid by-products, which is more superior than the existing SCR-NH3 denitrification catalyst.

[0043] In summary, the present invention has the advantages of low cost, scalable production, efficient ammonia synthesis, ammonia decomposition and SCR-NH3 selective catalytic reduction denitrification reaction, superior catalyst performance, high catalytic activity and efficiency, good stability, not easy to deactivate and poison, combinable and adjustable active substances, controllable loading amount, simple and convenient application process, etc.

[0044] In order to achieve the above and related purposes, one or more aspects of the present invention include the features that will be described in detail later. The following description and the accompanying drawings describe some exemplary aspects of the present invention in detail. However, these aspects indicate only some of the various ways in which the principles of the present invention can be used. In addition, the present invention is intended to include all of these aspects and their equivalents. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] By referring to the following description in conjunction with the accompanying drawings, and with a more complete understanding of the present invention, other objects and results of the present invention will become more clear and easy to understand. In the accompanying drawings:

[0046] Figure 1 Flow chart of a liquid-phase ammonia-related catalyst for an ammonia decomposition reaction according to an embodiment of the present invention;

[0047] Figure 2 Another flow chart of a liquid-phase ammonia-related catalyst for an ammonia decomposition reaction according to an embodiment of the present invention;

[0048] Figure 3 Flow chart of a liquid-phase ammonia-related catalyst for an ammonia synthesis reaction according to an embodiment of the present invention;

[0049] Figure 4 Another flow chart of a liquid-phase ammonia-related catalyst for an ammonia synthesis reaction according to an embodiment of the present invention;

[0050] Figure 5 Flowchart of a liquid-phase ammonia-related catalyst for SCR denitration reaction according to an embodiment of the present invention;

[0051] Figure 6 Another flow chart of using a liquid-phase ammonia-related catalyst for SCR denitration reaction according to an embodiment of the present invention;

[0052] Figure 7 This is another flow chart of using a liquid-phase ammonia-related catalyst for an SCR denitration reaction according to an embodiment of the present invention;

[0053] Figure 8 is a schematic diagram of the experimental device in Example 1 of the present invention;

[0054] Figure 9 Schematic diagram of the principle of the molten pool and the atomizing nozzle according to Example 2 of the present invention;

[0055] Figure 10 Schematic diagram of the principle of the experimental device according to Example 2 of the present invention. DETAILED DESCRIPTION

[0056] In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of one or more embodiments. However, it will be apparent that these embodiments may be practiced without these specific details.

[0057] In view of the problems of easy deactivation, poor stability, high preparation cost and poor catalytic effect of the catalysts for ammonia chemical reactions in the above-mentioned existing technologies, a liquid-phase ammonia-related catalyst and its application are proposed.

[0058] The specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0059] In order to illustrate the liquid phase ammonia-related catalyst and its application provided by the present invention, Figure 1 The process of using a liquid-phase ammonia-related catalyst for ammonia decomposition reaction according to an embodiment of the present invention is shown; Figure 2 Another process of using a liquid-phase ammonia-related catalyst for ammonia decomposition reaction according to an embodiment of the present invention is shown; Figure 3 The process of using a liquid-phase ammonia-related catalyst for an ammonia synthesis reaction according to an embodiment of the present invention is shown; Figure 4 Another process of using a liquid-phase ammonia-related catalyst for an ammonia synthesis reaction according to an embodiment of the present invention is shown; Figure 5 The process of using a liquid-phase ammonia-related catalyst for SCR denitration reaction according to an embodiment of the present invention is shown; Figure 6 Another process of using a liquid-phase ammonia-related catalyst for SCR denitration reaction according to an embodiment of the present invention is shown; Figure 7 Another process of using a liquid-phase ammonia-related catalyst for SCR denitration reaction according to an embodiment of the present invention is shown; Figure 8 The principle of the experimental device in Example 1 of the present invention is shown; Figure 9 The principle of the molten pool and atomizing nozzle according to Example 2 of the present invention is shown; Figure 10 The principle of the experimental device according to Example 2 of the present invention is shown.

[0060] like Figure 1-10 As shown, the liquid-phase ammonia-related catalyst provided by the present invention is made by dissolving at least two elements selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, gold, gallium, indium, tin, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, aluminum, sulfur, selenium, and tellurium in each other in liquid state; wherein the liquid-phase ammonia-related catalyst refers to a catalyst involving an ammonia reaction that is liquid under reaction conditions.

[0061] It should be noted that the liquid-phase ammonia-related catalyst provided by the present invention includes at least two of the aforementioned elements, which may be the corresponding elements in their simple form or compounds of the aforementioned elements, such as halides, preferably the corresponding elements in their simple form. The ratio of the elements in the liquid-phase ammonia-related catalyst is adjusted by weighing according to actual needs and is not particularly limited in the present invention.

[0062] As a preferred embodiment of the present invention, the content of each element accounts for 0.01-99.99at.% of the liquid-phase ammonia-related catalyst, where at. represents the atomic fraction; when the liquid-phase ammonia-related catalyst includes transition metal elements, the proportion of transition metal elements in the liquid-phase ammonia-related catalyst does not exceed 90at.%; wherein the transition metal elements include at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, and gold.

[0063] Specifically, the weight of each element converted from the corresponding substance accounts for 0.01-99.99at.% of the weight of the liquid-phase ammonia-related catalyst; when the liquid-phase ammonia-related catalyst includes a transition metal element, the weight of the transition metal element converted from the corresponding substance accounts for no more than 90at.% of the weight of the liquid-phase ammonia-related catalyst.

[0064] As a preferred embodiment of the present invention, one or at least two elements selected from manganese, iron, and ruthenium are selected as the first component;

[0065] Select one or at least two elements from gallium, indium, tin, lead, bismuth, lanthanum, cerium, and samarium as the second component;

[0066] The first component and the second component are dissolved in each other in a liquid state to prepare a liquid-phase ammonia-related catalyst.

[0067] As a preferred embodiment of the present invention, one or at least two elements selected from manganese, iron, and ruthenium are selected as the first component;

[0068] Select one or at least two elements from gallium, indium, tin, lead, bismuth, lanthanum, cerium, and samarium as the second component;

[0069] One or at least two elements are selected from lithium, sodium, potassium, rubidium, cesium, francium, magnesium, and calcium as the third component; or one or at least two elements are selected from lithium, sodium, potassium, rubidium, cesium, and francium as the third component; or one or at least two elements are selected from magnesium and calcium as the third component;

[0070] The first component, the second component, and the third component are dissolved in each other in a liquid state to prepare a liquid-phase ammonia-related catalyst.

[0071] Furthermore, manganese is selected as the first component, liquid metal gallium, indium, tin, and bismuth are selected as the second component, alkali metals lithium, sodium, and potassium, alkaline earth metals magnesium and calcium, other metals aluminum, and rare earth metals lanthanum, cerium, and samarium are selected as the optional third component. The above-mentioned LCs-NH3 (liquid-phase ammonia-related catalyst) must include a combination of at least one element of the first component and at least one element of the second component, and the ratio of the total elements of the second component is 35-99.99at.%; further, manganese and bismuth alloys are selected to form LCs-NH3, manganese and lanthanum alloys are selected to form LCs-NH3, manganese and cerium alloys are selected to form LCs-NH3, and manganese and samarium alloys are selected to form LCs-NH3.

[0072] As a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is a liquid in which all material components are mutually soluble, and is obtained by pre-dissolving at room temperature or pre-heating and melting; or, directly heating and melting to a liquid state under reaction conditions; or, mixing a source material containing the element selected as the liquid-phase ammonia-related catalyst with a carrier and a solvent of the catalyst to obtain a suspension; filtering and drying the suspension in sequence to obtain a catalyst precursor; calcining the precursor, and performing a reduction reaction in a reducing gas atmosphere to obtain a carrier-supported liquid-phase ammonia-related catalyst, and the liquid-phase ammonia-related catalyst is in a liquid state under reaction conditions.

[0073] Specifically, for example, when the elements selected as the liquid-phase ammonia-related catalyst include at least one element that is liquid at room temperature and at least one element that is solid at room temperature, the element that is liquid at room temperature or a liquid mixture formed by mixing at least two elements that are liquid at room temperature is used as a solvent, the element that is solid at room temperature is used as a solute, and the solute is dissolved in the solvent to obtain a liquid-phase ammonia-related catalyst;

[0074] When all elements selected as the liquid-phase ammonia-related catalyst are in solid state at room temperature, the elements selected as the liquid-phase ammonia-related catalyst are uniformly mixed to obtain a mixture, and the mixture is heated to at least 2° C. higher than the theoretical lowest melting point of the alloy phase diagram of the mixture, so that the mixture dissolves in each other in the liquid state to obtain a liquid-phase ammonia-related catalyst;

[0075] A source material containing an element selected as a liquid-phase ammonia-related catalyst is mixed with a catalyst carrier and a solvent to obtain a suspension; the suspension is filtered and dried in sequence to obtain a catalyst precursor; the precursor is calcined and subjected to a reduction reaction in a reducing gas atmosphere to obtain a carrier-supported liquid-phase ammonia-related catalyst.

[0076] As a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is a droplet-type catalyst when used; wherein,

[0077] The droplet diameter of the droplet-type catalyst is less than 0.1 mm;

[0078] The preparation method of the droplet-type catalyst is as follows:

[0079] Atomizing the liquid-phase ammonia-related catalyst into a droplet-type catalyst by any one of pressurization, dual-flow atomization, ultrasound, and centrifugation; or,

[0080] The liquid-phase ammonia-related catalyst is made into ultrafine powder by any one of liquid atomization followed by rapid cooling, electron beam rapid cooling and quenching, laser surface melting, and mechanical crushing, and the ultrafine powder is placed in a container and heated to form a droplet-type catalyst; or,

[0081] Loading the components of the liquid-phase ammonia-related catalyst on a carrier, and melting the components on the carrier by heating to form a droplet-type catalyst; or

[0082] The liquid phase ammonia-related catalyst is heated, evaporated, and then condensed to form droplets that reflux, thereby obtaining a droplet-type catalyst.

[0083] Specifically, the droplet diameter of the droplet-type catalyst is less than 0.1 mm, preferably a nanoparticle size of 1 nm to 100 nm (inclusive) or a microparticle size of 0.1 μm to 100 μm (inclusive). The method for forming the droplets of the catalyst includes: atomizing the catalyst liquid to form the droplets, the atomization method includes: pressurization, dual-flow (air flow or liquid flow / liquid flow) atomization, ultrasound, centrifugation; or prefabricating the catalyst ultrafine powder, introducing / entering / spraying into the container under reaction conditions, and being heated to form droplets; the preparation method of the ultrafine powder includes rapid cooling after liquid atomization, electron beam rapid cooling quenching, laser Surface melting, mechanical crushing, atomization methods include: pressurization, dual-flow (air flow or liquid flow / liquid flow) atomization, ultrasound, centrifugation, mechanical crushing includes: air flow mill, high-speed mechanical impact mill, vibration mill, stirred mill, ball mill, sand mill, cyclone mill, high-pressure roller (roller) mill, high-pressure water jet mill, high-pressure homogenization, ultrafine shearing, ultrasonic crushing; or first load the catalyst formula material on the carrier, heat and melt on the carrier after heating, and form melt droplets under the action of the surface tension of the catalyst material components and / or the carrier structure; or heat the catalyst to evaporate and then condense into droplets for reflux.

[0084] The application of the liquid-phase ammonia-related catalyst provided by the present invention is to apply the liquid-phase ammonia-related catalyst provided by the present invention as described above to an ammonia decomposition reaction, an ammonia synthesis reaction, or an SCR denitration reaction.

[0085] like Figure 1 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the ammonia decomposition reaction, comprising the following steps:

[0086] A1. Under the condition of reaction temperature of 500-1500℃, the reaction raw material NH3 is introduced into the bottom of the container containing liquid ammonia catalyst;

[0087] The bubbles of A2 and NH3 float up and come into contact with the liquid ammonia catalyst to generate a catalytic reaction, producing products H2 and N2;

[0088] A3. Separate the product H2, product N2 and unreacted NH3.

[0089] The preferred reaction temperature in step A1 is 650-1000°C.

[0090] like Figure 2 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the ammonia decomposition reaction, comprising the following steps:

[0091] B1, introducing the reaction raw material NH3 into a container filled with droplets of a liquid-phase ammonia-related catalyst and allowing the reaction to remain there for a first preset time, so that the reactant and the droplets of the liquid-phase ammonia-related catalyst come into interfacial contact, causing a catalytic reaction to occur, and generating products H2 and N2;

[0092] B2. Separate the product H2, product N2 and unreacted NH3, and collect the droplets of the liquid ammonia-related catalyst and separate them from the impurities for reuse.

[0093] like Figure 3 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the ammonia synthesis reaction, comprising the following steps:

[0094] C1. Under the conditions of a reaction temperature of 400-1000°C and a reaction pressure of 0.1-50 MPa, the mixed reaction gas obtained by mixing the reaction raw materials H2 and N2 is introduced into the bottom of a container containing a liquid ammonia-related catalyst;

[0095] C2, the bubbles of the mixed reaction gas float up and come into contact with the liquid phase ammonia catalyst interface, a catalytic reaction occurs, and the product NH3 is generated;

[0096] C3. Separate the unreacted reaction raw material H2, the unreacted reaction raw material N2 and the product NH3.

[0097] Wherein, in step C1, the preferred reaction temperature is 300-750°C.

[0098] like Figure 4 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the ammonia synthesis reaction, comprising the following steps:

[0099] D1, introducing the reaction raw materials H2 and N2 into a container filled with droplets of a liquid-phase ammonia-related catalyst, and allowing the reaction raw materials to stay for a predetermined time, so that the reaction raw materials and the droplets of the liquid-phase ammonia-related catalyst come into interfacial contact, a catalytic reaction occurs, and the product NH3 is generated;

[0100] D2. Separate the product NH3 and the unreacted reaction raw materials H2 and N2, and collect the droplets of the liquid phase ammonia-related catalyst and separate them from the impurities for reuse.

[0101] like Figure 5 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps:

[0102] E1. Under the condition of reaction temperature of 280-1200°C, the reaction raw materials NH3 and NO-containing reaction raw gas are introduced into the bottom of the container containing the liquid phase ammonia-related catalyst;

[0103] E2, the bubbles of the reaction raw material NH3 and the reaction raw material gas containing NO float up and come into interfacial contact with the liquid phase ammonia-related catalyst, and a catalytic reaction occurs. The gaseous products and unreacted products float to the liquid surface and are discharged after treatment to complete the SCR denitrification reaction.

[0104] In step E1, the preferred reaction temperature is 400-900°C, and the further preferred reaction temperature is 280-900°C.

[0105] like Figure 6 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps:

[0106] F1. Passing the reaction raw materials NH3 and the reaction raw material gas containing NO into a container filled with droplets of a liquid-phase ammonia-related catalyst and holding the container for a second preset time, so that the reaction raw materials come into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst and a catalytic reaction occurs;

[0107] F2. The gaseous products and unreacted gaseous reaction raw materials produced in the catalytic reaction are discharged after treatment, and the droplets of the liquid ammonia-related catalyst are collected and separated from the impurities before being reused.

[0108] like Figure 7 As shown, as a preferred embodiment of the present invention, the liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps:

[0109] G1. Spraying the reaction raw material NH3 and droplets of a liquid-phase ammonia-related catalyst into the flue gas containing the NOx reaction raw material gas, so that the reaction raw material NH3 and the flue gas containing the NOx reaction raw material gas come into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst, causing a catalytic reaction;

[0110] G2. The gaseous products and unreacted gaseous reaction raw materials produced in the catalytic reaction are discharged after treatment, and the droplets of the liquid ammonia-related catalyst are collected and separated from the impurities and unreacted solid reaction raw materials for reuse.

[0111] The first preset time, the second preset time, and the preset time mentioned above in the present invention can be set according to actual conditions, and the present invention does not impose any special limitation on this.

[0112] As a preferred embodiment of the present invention, the material components of the liquid-phase ammonia-related catalyst are pre-loaded on the surface of a solid support and introduced into a reaction vessel in solid form. Under reaction conditions, the surface material components of the solid support are heated and melted into droplets, so that the gaseous reactants flow through the solid support and fully contact the droplets on the solid support.

[0113] The reaction vessel is a fluidized bed reactor, and the liquid ammonia-related catalyst reacts with the gaseous reactants in the fluidized bed in the form of liquid droplets; or,

[0114] The reaction vessel is a fixed bed reactor. The catalyst loaded on the surface of the solid carrier in the form of droplets is pre-filled in the fixed bed reactor. The gaseous reactants flow through the fixed bed to cause catalytic reaction.

[0115] In order to better illustrate the application effect of the liquid-phase ammonia-related catalyst provided by the present invention, the following specific examples are provided.

[0116] Example 1:

[0117] The catalytic reaction experimental device uses a vertical tube furnace, a stainless steel outer sleeve + a quartz crucible, and other supporting devices (the experimental device is existing technology, so it is not described in detail).

[0118] The stainless steel casing prevents the potential safety hazards of quartz cracking and alloy leakage at high temperatures. The quartz crucible, serving as the primary reactor, eliminates interference from metal containers in catalysis. Quartz's inertness essentially does not react with the metal-based alloy and inorganic salt catalysts selected for this example. Unless otherwise specified, the primary reactor is a quartz crucible with a reactor diameter ID = 15 mm. Multiple reactors are mounted on a bracket, enabling catalytic experiments with 1-10 different catalyst formulations to be conducted simultaneously. The bracket is placed in a multi-stage controlled heating vertical tubular furnace, with the bracket's bottom supported and insulated by ceramic insulation.

[0119] Reactions were conducted separately in bubble columns, with the length of the bubble column measured from the gas bubbling point at the bottom of the crucible to the top of the constant-temperature heating zone. Thermal insulation at the upper and lower ends of the constant-temperature heating zone in the tubular furnace heating zone was provided by multiple layers of insulation, such as mica and asbestos, placed on the top of the crucible, and ceramic insulation at the bottom of the crucible. A 30mm thick alloy melt, intersecting the insulation barrier, outside the heating zone minimized headspace pure heat reactions. The crucible outside the insulation barrier was exposed to air and maintained cool by an external fan. The reactor headspace effect above the melt surface was further corrected using reaction data from selected inert metals. K-type thermocouples inserted into the melt measured the melt temperature in real time at multiple points during heating, holding, and bubbling reactions.

[0120] The mixed gas is introduced into the reactor from above through a fine quartz tube via a pipeline using a gas mass flow meter MFC, and analyzed by an online mass spectrometer MS and a gas chromatograph GC.

[0121] The schematic diagram of the experimental device is as follows: Figure 5 shown.

[0122] Ammonia decomposition reaction.

[0123] Before the catalytic experiment begins, the alloy is melted. The materials are loaded into the molten pool according to the recipe and the loading amount of each material. The temperature is raised in stages to 1050°C and held for 12 hours while maintaining an Ar gas purge. The catalyst is then reduced with hydrogen to produce a liquid-phase ammonia-related catalyst LCs-NH3 melt, which is then cooled to the reaction temperature.

[0124] The catalyst formulations (5 groups in total) are as follows: 30Mn-70Bi, 20Mn-5Cu-75Bi, 25Mn-75Bi, 18Mn-2Li-80Bi, and the comparative element Sn. The 30Mn-70Bi formula represents a Mn atomic fraction of 30 at.%, and a Bi atomic fraction of 70 at.%. Subsequent expressions of the contents are expressed in this manner unless otherwise specified. The reaction pressure was set at 0.1 MPa. After purging and pretreatment, the experimental apparatus was introduced with a 30 sccm mixture of NH3 (feed ratio 32% NH3, 68% Ar) as the reaction raw material. The vent pipe diameter ID = 2 mm (unless otherwise specified, this diameter is used for similar apparatuses). The catalytic performance of each catalyst at reaction temperatures of 900°C and 950°C was examined in a 160 mm bubble column. The conversion rates are shown in Table 1.

[0125] Temperature Metal and alloy formulations Ammonia decomposition conversion rate % 900 30Mn-70Bi 61.70 900 20Mn-5Cu-75Bi 66.19 900 25Mn-75Bi 65.62 900 18Mn-2Li-80Bi 67.55 900 Sn 1.70 950 30Mn-70Bi 92.09 950 20Mn-5Cu-75Bi 97.83 950 25Mn-75Bi 87.78 950 18Mn-2Li-80Bi 99.58 950 Sn 3.07

[0126] Table 1

[0127] The catalytic performance of the 18Mn-2Li-80Bi catalyst at a reaction temperature of 950°C was investigated in a 300 mm bubble column, as shown in Table 2.

[0128] Temperature ℃ / bubble column height Metal and alloy formulations Ammonia decomposition conversion rate % 950 / 160 18Mn-2Li-80Bi 99.58 950 / 300 18Mn-2Li-80Bi 99.99 30

[0129] Table 2

[0130] At a reaction temperature of 800°C, the highest conversion rate among the above catalysts, 18Mn-2Li-80Bi, was only 12.63%, while the others were all below 10%. At the same time, at reaction temperatures above 950°C, the best-performing catalyst, 18Mn-2Li-80Bi, within the data error range, could no longer improve the conversion rate. When the bubble column height was increased to 300mm, the conversion rate of 18Mn-2Li-80Bi reached 99.99%.

[0131] At a reaction temperature of 600°C and other conditions remaining unchanged, 8000V plasma was used to assist in the activation of the raw gas, and the feed ratio was 67% NH3 and 33% Ar18Mn-2Li-75Bi, resulting in an ammonia decomposition conversion rate of 89.21%.

[0132] In the same temperature range (800-950°C) mentioned above, the Mn-Sn, Mn-In, Mn-Ga, and Mn-Pb combinations still exhibit lower ammonia decomposition conversion rates than the Mn-Bi combination, even when alkali metals such as lithium, sodium, potassium, rubidium, cesium, and francium, alkaline earth metals such as magnesium and calcium, or other metals such as aluminum are added as third components. These alloy combinations also exhibit significantly higher catalytic activity than pure Sn above 850°C.

[0133] Catalyst formula: 16.7Fe-83.3Ce combination. Under the same conditions, the alloy melt catalytic ammonia decomposition conversion rate at 900 and 950℃ was 33.1% and 62.8% respectively.

[0134] Catalyst formula: 0.01Ru-99.99Bi. Under the same conditions, the alloy melt catalytic ammonia decomposition conversion rate is 8.4% and 15.6% at 900 and 950℃ respectively.

[0135] Catalyst formula: metal modified ZSM-5 molecular sieve catalyst Ni 0.03 Mo 0.01 Bi 0.96 / ZSM-5, Ni-Mo-Bi alloy as droplets. A liquid-phase ammonia-related catalyst LCs-NH3 supported on a carrier. The catalyst formulation is loaded onto the carrier and melted on the carrier after heating. The low-load catalyst material components form melt droplets under the influence of surface tension and / or the carrier structure. The details are as follows:

[0136] The 3Ni-1Mo-96Bi catalyst was liquid at 500°C using in-situ high-temperature XRD and in-situ high-temperature energy dispersion spectroscopy. Therefore, the supported metal element concentration and relative atomic mass were calculated according to the formula, and then the metal ion mass of the corresponding salt was weighed: nickel nitrate hexahydrate (Ni(NO3)2·6H2O), ammonium heptamolybdate ((NH4)6Mo7O 24 ) and bismuth nitrate (Bi(NO3)3) are dispersed in a 1% dilute nitric acid solution at a Ni:Mo:Bi ratio of 3:1:96. The solution is ultrasonically vibrated for 30 minutes, and the above solution is added dropwise to twice the mass of ZSM-5 molecular sieve and stirred evenly for wet impregnation. The above sample is sealed and aged for 24 hours. It is then placed in an oven at 105°C for 24 hours, ground evenly in a mortar, and placed in a tube furnace. The above modified catalyst is reduced with H2 at 550°C for 5 hours, cooled, and ground again to obtain the ZSM-5 supported metal modified ZSM-5 molecular sieve catalyst 3Ni-1Mo-96Bi / ZSM-5, which is stored in a sealed and dry place in a stainless steel storage tank.

[0137] The reaction is carried out in a quartz crucible with a total length of 1000 mm. A gas mass flowmeter (MFC) is used to introduce the mixed raw gas into the center of the crucible from above via a thin quartz tube. The length of the reaction zone matches the length of the constant-temperature heating zone, which is insulated by a tube furnace heating zone (600 mm long) at the top and bottom, and by multiple layers of insulation, such as mica, ceramic, and asbestos, at the top and bottom of the crucible (150 mm and 250 mm in length, respectively). Outside the insulation, the top and bottom of the crucible are exposed to air and maintained cool by an external fan to minimize the effects of pure headspace reactions. Headspace effects are further corrected using reaction data from selected inert metals. K-type thermocouples in the crucible measure the temperature at multiple points in real time during the reaction. The reaction pressure was set to 0.1 MPa, the reaction temperature was 900 and 950 ° C, and after the above experimental device was purged, NH3 mixed gas 600 sccm (feed ratio 32% NH3, 68% Ar) was entrained and the above catalyst powder was sprayed in at a rate of 20 mg / min. The test results were as follows:

[0138] As shown in Table 3:

[0139] Temperature Metal and alloy formulations Ammonia decomposition conversion rate % 900 3Ni-1Mo-96Bi 53.8 950 3Ni-1Mo-96Bi 94.5

[0140] Table 3

[0141] The catalyst powder was collected regularly and added back into the system, and the catalytic efficiency remained unchanged after 12 hours.

[0142] Catalyst formula: 30Mn-70Bi, 18Mn-82Bi, pressure 0.1MPa, the experimental apparatus was changed to ID=180mm graphite crucible, the raw gas NH3 was supplied from the bottom through a ceramic aeration plate (aeration plate diameter 150mm, micropore diameter ~10um), the gas flow rate was 12SLM, and the catalytic performance of each catalyst at reaction temperatures of 950℃, 850℃, and 750℃ was investigated in a 100mm bubble column. The conversion rates were 100%, 100% and 58% respectively within the error range.

[0143] Compared with the catalytic effect of the aforementioned ID=2mm vent tube, the catalytic efficiency is greatly improved, and the reaction temperature is further reduced, reflecting the rapid improvement of the catalytic efficiency after the catalytic area is increased.

[0144] Catalyst formula: 18Mn-82Bi / ZSM-5, manganese nitrate (Mn(NO3)2) and bismuth nitrate (Bi(NO3)3) are dispersed in a 2% dilute nitric acid solution at a Mn:Bi ratio of 30:70. The solution is ultrasonically vibrated for 30 minutes, and the above solution is added dropwise to 2 times the mass of molecular sieve ZSM-5 and stirred evenly for wet impregnation. The above sample is sealed and aged for 24 hours. It is then placed in an oven at 105°C for 24 hours, ground evenly with a mortar, and placed in a modified catalyst. The above catalyst is reduced with H2 in a 550°C tubular furnace for 5 hours, cooled, and ground again to obtain a Mn-Bi catalyst Mn supported on a molecular sieve. 0.3 Bi 0.7 / ZSM-5, stored in a sealed and dry place in a storage tank. The reaction was carried out in a quartz crucible with a total length of 1000mm, and the reaction zone was filled with 100mm quartz beads (OD = 30um), 400mm catalyst Mn 0.3 Bi 0.7 / ZSM-5, and 100mm quartz beads (OD=30μm). A mass flowmeter (MFC) was used to introduce the mixed raw gas from the bottom of the crucible. The length of the reaction zone matched the length of the constant-temperature heating zone, which was insulated by a tube furnace heating zone (600mm long) at the top and bottom, and by multiple layers of insulation, such as mica, ceramic, and asbestos, at the top and bottom of the crucible (150mm and 250mm long, respectively). Outside the insulation, the top and bottom of the crucible were exposed to air and kept cool by an external fan to minimize the effects of pure headspace reactions. Headspace effects were further corrected using reaction data from selected inert metals. A K-type thermocouple in the crucible measured the temperature in real time during the reaction. The reaction pressure was set at 0.1MPa and the reaction temperatures were 850 and 775°C. After purging the experimental apparatus, 600sccm of pure NH3 gas was introduced, resulting in an ammonia decomposition conversion of 100%. Compared with the catalytic effect of the aforementioned ID=2mm vent tube, the catalytic efficiency is greatly improved, and the reaction temperature is further reduced, reflecting the rapid improvement of the catalytic efficiency after the catalytic area of ​​the droplet catalyst is increased.

[0145] Comparative Example 1

[0146] Wu Xiaoman, Li Xuefeng, and Zhang Hongbin. Preparation of Ruthenium / Carbon Nanotubes by Liquid-Phase Reduction and Their Catalytic Performance for Ammonia Decomposition. Precious Metals, Vol. 31, No. 3, August 2010, pp. 1-6.

[0147] Ru / CNTs were prepared using the impregnation method and the ethylene glycol liquid-phase reduction deposition method, respectively. The specific steps are as follows: ① 0.7067g of RuCl3·H2O (≥35%) was loaded onto 0.5000g of purified CNTs using an isochoric impregnation method in acetone (or water). After drying, the mixture was treated at 673K ​​under a stream of pure H2 for 4 hours to obtain x% Ru / CNTs (w). ② 0.2440mg of RuCl3·H2O was dissolved in 50ml of ethylene glycol. 1.700g of CNTs was then added to the ruthenium-ethylene glycol solution to form a uniform suspension. The suspension was then heated to 433K under reflux in an oil bath with stirring until the solution turned light yellow-brown. The solution was immediately removed, cooled, and the solid fraction was filtered and washed with deionized water to obtain x% Ru / CNTs (oh). The optimal range of x% was 3-6%, with 4.2% being the preferred value. 873K, space velocity GHSV = 30000 mL / h·g, 4.2% Ru / CNTs(OH) ammonia decomposition conversion rate 98%.

[0148] Compare:

[0149] In comparative example 1, the material cost of the 4.2% ruthenium component of the catalyst is 4,620 yuan / kg based on the ruthenium price of 110 yuan / g, and the preparation cost is 6,600 yuan / kg. The material cost of the 18Mn-2Li-75Bi alloy in Example 1 of the present invention is less than 50 yuan / kg, and considering the melt preparation, the direct cost is less than one percent of that of the Ru / CNTs catalyst.

[0150] As mentioned above, the raw material price of Bi / Mn metal is less than 0.05 / g, which is a few hundredths or even a few thousandths of that of precious metal dehydrogenation catalysts. Together with Li, the total cost of low-cost melting preparation of the alloy is ~0.05 / g. When the vent hole diameter in Example 1 is 2 μm, it is estimated that the diameter of a single bubble is approximately 0.1 cm, the residence time of the melt at 150 mm is approximately 1 s, the heated raw material volume is increased by 4 times, and the reaction volume is increased by 1.25 times, or 5 times. For large-scale production, assuming a 25% bubble occupancy rate in the melt, a single bubble requires 2 ml of melt, and the melt density is approximately 9 g / ml. The annual catalyst replacement rate does not exceed 2%, and considering annual depreciation, it is calculated as 10%. With an annual production of 300 days, each catalyst unit can produce 12,920 g of hydrogen. The product / mass catalytic efficiency of Comparative Example 1 is approximately 4 g of hydrogen / g catalyst / hour. With an annual production of 300 days, based on a conventional catalyst life of 6 months and two replacements, and considering a precious metal recycling and regeneration factor of 0.5, the total annual maintenance cost is 6.6 yuan / g, and 28.8 kg of hydrogen is produced per gram of catalyst per year, resulting in a hydrogen production of 4,363 g per catalyst unit. Given similar catalyst embrittlement effects, the unit cost of Example 1 is less than one-third of that of Comparative Example 1. Furthermore, according to the experimental results of the aeration plate device, the cost can be reduced by another 5-10 times.

[0151] In this embodiment, Ni 0.03 Mo 0.01 Bi 0.96 The catalytic efficiency of the ZSM-5 liquid droplet alloy is 9600 ml / g·h, which, while lower than that of Comparative Example 1, is significantly higher than that of the bubbling method for the Mn-Bi alloy melt in this example. Furthermore, the catalyst can be collected and reused, with the catalyst cost primarily consisting of collection and recycling costs and financial costs. The mass production collection cost is no more than 0.01 yuan / kg, and the financial depreciation is significantly lower than that of the bubbling method for the Mn-Bi alloy melt in this example. Based on this calculation, each catalyst can produce 10,700 g of hydrogen, with a catalyst cost of 93.4 yuan per ton of hydrogen, lower than existing commercial catalysts. Scaled-up production could potentially increase efficiency by 1-10 times.

[0152] Example 2

[0153] SCR-NH3 denitrification reaction:

[0154] Bubble column:

[0155] 5Mn-95Bi, 10Mn-1Ce-89Bi, and 18Mn-58Bi-24Sn alloy catalysts were refined as described above. The reaction pressure was set at 0.1 MPa. After purging and pretreatment, a reaction raw material mixed gas (feed ratio of 2% NH3, 2% NO, 68.2% Ar) was introduced into the above experimental apparatus. The catalytic performance of each catalyst at various reaction temperatures was examined in a 150 mm bubble column. The conversion rates are shown in Table 4.

[0156] Temperature Metal and alloy formulations NO conversion rate % 330 Sn 0.97 330 5Mn-95Bi 36.5 480 Sn 14.8 480 5Mn-95Bi 59.2 480 10Mn-1Ce-89Bi 71.6 480 18Mn-58Bi-24Sn 95.4 600 Sn 2.3 600 5Mn-95Bi 93.1 600 10Mn-1Ce-89Bi 98.7 600 18Mn-58Bi-24Sn 99.9

[0157] Table 4

[0158] After 100 h of reaction, the catalytic efficiency did not change.

[0159] When 2% SO2 is added to the reaction raw material mixed gas, the catalytic efficiency does not change much.

[0160] 18Mn-58Bi-24Sn alloy was refined and the reaction pressure was set at 0.1 MPa. After purging and pretreatment, 60 sccm of simulated dusty coal-fired flue gas was introduced into the experimental apparatus. The catalytic performance of the catalyst at a reaction temperature of 480°C was examined in a 300 mm bubble column. After 120 hours of reaction, no NO was detected, but a small amount of carbon and dust accumulated on the filter of the outlet pipe.

[0161] Atomized droplets (centrifugal atomization):

[0162] Before the catalytic experiment begins, the alloy is melted (to prepare the catalyst). The catalyst components are then added to a graphite melt according to the recipe. The temperature is then raised in stages to 1050°C and held for 4 hours while maintaining an Ar gas purge. The melt is then reduced with hydrogen to a catalyst melt, which is then cooled to the reaction temperature. The melt is then placed in an autoclave with a maximum operating pressure of 8 MPa and equipped with an atomizing nozzle.

[0163] Reactions were conducted in quartz crucibles with total lengths of 800, 1200, and 1600 mm, respectively. Unless otherwise specified, the reactor diameter (ID) was 25 mm, and the quartz crucible length was 1200 mm. Catalyst droplets from the molten pool were sprayed into the crucible from the top. Simultaneously, a mass flowmeter (MFC) was used to introduce the mixed feed gases from above through a pipeline via a thin quartz tube to the measured temperature point within the crucible's reaction zone. The length of the reaction zone coincided with the length of the constant-temperature heating zone, which was insulated by the upper and lower ends of a tubular furnace heating zone (effective lengths of 400, 800, and 1200 mm) and by multiple layers of insulation, such as mica, ceramic, and asbestos, at the top and bottom of the crucible (lengths of 150 mm and 250 mm, respectively). Outside the insulation layer, the crucible's top and bottom were exposed to air and kept cool by an external fan to minimize the effects of pure headspace heat reactions. Headspace effects were further corrected using reaction data from selected inert metals. The K-type thermocouple in the crucible measures the temperature at multiple points in real time during the reaction.

[0164] The analysis was performed using an online mass spectrometer (MS) and a gas chromatograph (GC).

[0165] like Figure 6 and Figure 7 As shown, the reaction pressure is set to 0.1 MPa. After the above experimental device is purged, 8Mn-10Ni-72Ce and 18Mn-58Bi-24Sn catalyst droplets are sprayed from the top respectively. The droplets are formed by centrifugal atomization of the melt drawn out from the 0.2 MPa high-pressure molten pool. The average particle size of the droplets is 20 μm according to calculation and prior laser reflection measurement. The injection amount is 40 mg / min. At the same time, the reaction raw material mixture of 1 sccm NH3, 1 sccm NO, and 8 sccm Ar is introduced into the measured temperature point in the reaction zone. The catalytic performance of the catalyst at a reaction temperature of 650°C is examined. The results show that the NO conversion rates are 99.99% and 99.97%.

[0166] After 10 h of reaction, the catalytic efficiency did not change.

[0167] When 1 sccm SO2 is added to the reaction raw material mixture, the catalytic efficiency does not change much.

[0168] With the control Sn droplets, the NO conversion was less than 1%.

[0169] Atomized droplets (air flow atomization):

[0170] The quartz crucible was 1600 mm long and contained an 18Mn-58Bi-24Sn alloy. Catalyst droplets were atomized from a 0.8 MPa high-pressure molten pool using a 0.4 MPa high-pressure nitrogen nozzle. Calculated and pre-measured by laser reflectometry, the average droplet size was 20 μm. The injection rate was 40 mg / min, and the top diameter was increased to allow for horizontal spraying. The high-pressure nitrogen flow was swirled, and 600 sccm of simulated dusty coal flue gas was introduced into the 480°C reaction zone at the measured temperature. All other conditions were the same as above. Neither NO nor dust was detected. The reaction gases were stopped and replaced with nitrogen. The solid matter at the bottom was collected to yield nanocarbon, dust, and the catalyst alloy.

[0171] Comparative Example 2

[0172] The experimental apparatus of Example 1 was used to refine an 18Mn-58Bi-24Sn alloy. The reaction pressure was set at 0.1 MPa. After purging and pretreatment, 60 sccm of simulated dusty coal-fired flue gas was introduced. The catalytic performance of the catalyst at a reaction temperature of 480°C was examined in a 300 mm bubble column. After 120 h of reaction, no NO was detected, but a small amount of carbon and dust accumulated on the filter of the outlet pipe.

[0173] According to the bubble occupancy rate of 25% in the melt, the average volume expands by 2.5 times upon heating, the vent tube orifice diameter ID = 2 mm, the single bubble diameter d ~ 1 cm, the 30 cm melt residence time t ~ 2 s, the bubble gas volume v ~ 0.5 ml, the catalyst alloy density ~ 9 g / ml, and the flue gas / mass catalytic efficiency 20 ml flue gas / g catalyst·h; the mass catalytic efficiency in the airflow atomization method of this embodiment is 15000 ml flue gas / g catalyst·h, which is much better than that of Comparative Example 2.

[0174] In the air flow atomization method of this embodiment, only 1728g of catalyst is used in 30 days, and the catalyst can be reused after separation of by-products. The cost of the catalyst mainly lies in the atomization and collection cycle costs, among which the atomization energy consumption cost is the main one, which does not exceed 8 yuan / kg. According to the present embodiment, the cost of each catalyst (agent) can treat 1905L of dust-containing coal-fired flue gas, and the treatment efficiency can be increased by 10-100 times after scale-up.

[0175] Comparative Example 3

[0176] SCR-NH3 denitrification. Commercially available honeycomb catalyst, active component (V2O5) carrier (WO3 / TiO2), flow area approximately 80%, simulated coal-fired flue gas denitrification at 480°C.

[0177] High-temperature denitrification followed by low-temperature dust removal. Honeycomb catalyst, active component (V2O5) carrier (WO3 / TiO2), with a flow area of ​​approximately 80%, is wear-resistant and easy to regenerate.

[0178] High-temperature electrostatic dust removal followed by low-temperature denitrification process. The catalyst is as above.

[0179] The denitration catalyst in Comparative Example 2 was exposed to high-concentration dust and flue gas for extended periods, resulting in severe catalyst wear, clogging, and poisoning. This shortened catalyst lifespan, reduced denitration efficiency, and increased operating costs. Spent vanadium-titanium catalysts are hazardous waste, toxic to the environment and humans. Their high density makes them difficult to disassemble. While Comparative Example 2 achieved some effect in extending catalyst lifespan, the dust removal still failed to prevent wear, clogging, and poisoning. The dust removal and denitration processes remained separate devices, occupying a large footprint, resulting in poor synergy and poor ultra-low emission stability. Pollution from spent vanadium-titanium catalysts persisted.

[0180] By comparison, it can be seen that if the existing denitrification process such as Comparative Example 3 adopts a high-temperature denitrification followed by a low-temperature dust removal process, it will inevitably cause the denitrification catalyst to be in a high-concentration dust and flue gas working condition for a long time. Flue gas dust is an important cause of catalyst wear, clogging, and poisoning, which shortens the catalyst life, reduces denitrification efficiency, and increases operating costs. Since the catalysts prepared in Examples 1 and 2 of the present invention do not deactivate for a long time, it shows that the liquid high-density alloy of the catalytic system can withstand high temperatures and high dust and high ash - the dust quickly floats out of the melt, does not affect the catalytic activity, and can also resist the poisoning of sulfur oxides; the catalyst in the embodiment of the present invention does not deactivate for a long time, which shows that the liquid droplet alloy of the catalytic system can withstand high temperatures and high dust and high ash; therefore, it does not affect the catalytic activity and can be arranged in the high-temperature section before dust removal; there is no ammonia residue; there is no toxic metal pollution; compared with Comparative Examples 2 and 3, this embodiment also has the function of removing dust. Therefore, the above-mentioned catalytic system is much better than the existing catalyst in terms of SCR-NH3 denitrification performance.

[0181] Example 3

[0182] Ammonia synthesis reaction.

[0183] The liquid phase ammonia-related catalyst LCs-NH3 was prepared before the catalytic experiment began.

[0184] 8Mn-8Li-84Bi alloy catalyst. First, melt the alloy. Add the components according to the recipe and loading amount into a quartz crucible. Raise the temperature in stages to 1050°C and hold for 12 hours while maintaining an Ar purge. Reduce with hydrogen to obtain a liquid-phase ammonia-related catalyst LCs-NH3 melt. Cool the melt to the reaction temperature.

[0185] Droplet-type 3Ni-1Mo-96Bi catalyst. First, calculate the supported metal element concentration and relative atomic mass according to the formula, and then weigh the metal ion mass of the corresponding salt: nickel nitrate hexahydrate (Ni(NO3)2·6H2O), ammonium heptamolybdate ((NH4)6Mo7O 24) and bismuth nitrate (Bi(NO3)3) are dispersed in a 1% dilute nitric acid solution at a Ni:Mo:Bi ratio of 3:1:96. The solution is ultrasonically vibrated for 30 minutes, and the above solution is added dropwise to twice the mass of ZSM-5 molecular sieve and stirred evenly for wet impregnation. The above sample is sealed and aged for 24 hours. It is then placed in an oven at 105°C for 24 hours, ground evenly in a mortar, and placed in a tube furnace. The above modified catalyst is reduced with H2 at 550°C for 5 hours, cooled, and ground again to obtain the ZSM-5 supported metal modified ZSM-5 molecular sieve catalyst 3Ni-1Mo-96Bi / ZSM-5, which is stored in a sealed and dry place in a stainless steel storage tank.

[0186] A liquid phase ammonia catalyst containing a mixed halide salt containing Mn, Li, and K. Directly heat to the reaction temperature and stabilize.

[0187] Ammonia synthesis was carried out in a quartz crucible by loading the above-mentioned 15MnCl2-30LiCl-55KCl mixed salt formula and the smelted 8Mn-8Li-84Bi alloy catalyst into the crucible at a loading amount of 30 cm in liquid column measurement length. The catalytic reactions were carried out at atmospheric pressures of 450°C and 500°C, with a reaction gas flow rate of 30 sccm and an N:H ratio of 1:3.17.

[0188] The results are shown in Table 5:

[0189] Temperature Metal and alloy formulations Synthetic ammonia yield% 450 8Mn-8Li-84Bi 0.06 450 <![CDATA[15MnCl2-30LiCl-55KCl]]> 0.37 500 8Mn-8Li-84Bi 0.11 500 <![CDATA[15MnCl2-30LiCl-55KCl]]> 0.38

[0190] Table 5

[0191] The reaction was performed using a micro-high-pressure reactor. The above-mentioned 15MnCl2-30LiCl-55KCl salt mixture was loaded into a crucible with a liquid column length of 30cm. The catalytic reaction was carried out at 450°C, a reaction gas flow rate of 30sccm, and an N:H ratio of 1:3.17. The pressures for the pressurized reactions were 0.1, 1, and 5MPa, respectively; and 370°C at 10MPa. The results are shown in Table 6:

[0192] Temperature Pressure MPa Synthetic ammonia yield% 450 0.1 0.37 450 1 1.94 450 5 2.93 370 10 4.5

[0193] Table 6

[0194] Alloy 8Mn-8Li-84Bi and molten salt 15MnCl2-30LiCl-55KCl droplets were formed as in Example 2, and the droplet-type 3Ni-1Mo-96Bi catalyst was prepared as above.

[0195] Ammonia synthesis was carried out using a quartz crucible at atmospheric pressures of 450 and 500°C, with a reaction gas flow rate of 30 sccm and an N:H ratio of 1:3.17. Alloy droplets were formed by centrifugal atomization from a melt drawn from a 0.2 MPa high-pressure molten pool. Calculations and prior laser reflection measurements showed that the average droplet size was 20 μm, and the injection rate was 40 mg / min. 3Ni-1Mo-96Bi / ZSM-5 was simultaneously injected at a rate of 40 mg / min for catalytic reaction. 15MnCl2-30LiCl-55KCl mixed molten salt droplets were formed by centrifugal atomization from a melt drawn from a 0.2 MPa high-pressure molten pool. Calculations and prior laser reflection measurements showed that the average droplet size was 60 μm, and the injection rate was 50 mg / min. The results are shown in Table 7.

[0196] Temperature Metal and alloy formulations Synthetic ammonia yield% 450 8Mn-8Li-84Bi 0.14 450 3Ni-1Mo-96Bi / ZSM-5 0.23 450 <![CDATA[15MnCl2-30LiCl-55KCl]]> 0.88 500 8Mn-8Li-84Bi 0.11 500 3Ni-1Mo-96Bi / ZSM-5 0.25 500 <![CDATA[15MnCl2-30LiCl-55KCl]]> 0.71

[0197] Table 7

[0198] Catalyst formulation: Molecular sieve-supported mixed salt catalyst 15MnCl2-30LiCl-55KCl / ZSM-5. MnCl2, LiCl, and KCl are dissolved in water according to the stoichiometric ratio to form a 1% dilute solution. The solution is ultrasonically shaken for 60 minutes. The aqueous solution is then added dropwise to a double-mass molecular sieve ZSM-5 and stirred evenly for wet impregnation. The sample is sealed and allowed to stand for 24 hours. The sample is then dried in a vacuum oven at 105°C for 24 hours and ground evenly in a mortar to obtain the molecular sieve-supported mixed salt catalyst 15MnCl2-30LiCl-55KCl / ZSM-5. This is then stored in a sealed, dry place in a storage tank. The reaction was conducted in a 300mm-long quartz crucible. The reaction zone was filled with 50mm quartz beads (OD = 30µm), 200mm catalyst, and 50mm quartz beads (OD = 30µm). A mass flowmeter (MFC) was used to introduce the mixed raw gas into the crucible from the bottom. The length of the reaction zone matched the length of the constant-temperature heating zone, which was insulated by a tubular furnace at the top and bottom, and by multiple layers of insulation, such as mica, ceramic, and asbestos, at the top and bottom of the crucible (150mm and 250mm in length, respectively). Outside the insulation, the top and bottom of the crucible were exposed to air and kept cool by an external fan to minimize the effects of pure headspace reactions. Headspace effects were further corrected using reaction data from selected inert metals. A K-type thermocouple in the crucible measured the temperature in real time during the reaction. The reaction pressure was set at 0.1 MPa and the reaction temperature was set at 450°C. After purging, the reaction gas was introduced into the experimental apparatus at a flow rate of 60 sccm. The N:H ratio was 1:3.1, and a synthetic ammonia yield of 0.93% was obtained, reflecting the improvement of the catalytic efficiency after the catalytic area of ​​the droplet catalyst was increased.

[0199] Comparative Example 4

[0200] The current industrial ammonia synthesis Haber-Bosch process is implemented under high temperature and high pressure conditions (450-550°C, pressure 10-30 MPa), consuming 1%-2% of the world's total energy supply; at the same time, it emits approximately 500 million tons of carbon dioxide each year, accounting for about 1.8% of global carbon dioxide emissions. Fused iron catalysts are still the mainstream catalysts in industrial production.

[0201] Comparison: Exploring efficient ammonia synthesis catalysts other than molten iron catalysts is a relentless pursuit in the chemical industry. Since low temperatures favor higher conversion rates, better catalysts must operate at lower temperatures. The 8Mn-8Li-84Bi alloy and the 15MnCl2-30LiCl-55KCl molten salt catalysts in this embodiment of the present invention both have melting points below 300°C, while the 3Ni-1Mo-96Bi / ZSM-5 catalyst has a melting point of ~440°C. Compared to Comparative Example 4, this embodiment demonstrates the superior catalytic performance of each catalyst. Furthermore, the liquid drop catalyst of this embodiment, with the same formulation, exhibits higher efficiency than conventional melt catalysts.

[0202] It can be seen from the above specific embodiments that the liquid-phase ammonia-related catalyst and its application provided by the present invention greatly reduce the preparation cost of the catalyst by replacing precious metals with cheap and resource-rich elements; and can be multi-combined as needed to play the synergistic catalytic role of multiple elements and components; it is prepared by dissolving the substances in the formula in liquid state, and the preparation method is simple and the quality is uniform and controllable, which is suitable for large-scale production; the liquid-phase ammonia-related catalyst provided by the present invention has high activity and efficiency, especially the efficiency of synthesizing ammonia is better than traditional molten iron catalysts and expensive ruthenium catalysts, and has high stability, is not easy to deactivate and poison, and can also adapt to harsh working conditions, especially for catalytic denitrification. Most of the existing denitrification adopts low-temperature denitrification after dust removal. At this time, the Ru catalyst is expensive and not very active. The liquid-phase ammonia-related catalyst provided by the present invention can be directly sprayed into the flue gas with ammonia in the form of liquid droplets, or the flue gas can be bubbled from the bottom of the liquid-phase catalyst. During use, it can withstand high temperatures and high dust and ash without affecting the catalytic activity. It can also resist the poisoning of sulfur oxides, so it can be arranged in the high-temperature section before dust removal; the catalyst is easy to separate from the solid by-products, which is more superior than the existing SCR-NH3 denitrification catalyst.

[0203] The liquid-phase ammonia-related catalyst and its applications according to the present invention have been described above by way of example with reference to the accompanying drawings. However, those skilled in the art will appreciate that various modifications may be made to the liquid-phase ammonia-related catalyst and its applications according to the present invention without departing from the scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the contents of the appended claims.

Claims

1. A liquid-phase ammonia-related catalyst, characterized in that: The catalyst is prepared by dissolving at least two elements selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, gold, gallium, indium, tin, lead, bismuth, lanthanum, cerium, praseodymium, neodymium, samarium, europium, lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, aluminum, sulfur, selenium, and tellurium in each other in liquid state; wherein the liquid-phase ammonia-related catalyst refers to a catalyst involving an ammonia reaction that is liquid under reaction conditions.

2. The liquid-phase ammonia-related catalyst according to claim 1, characterized in that The content of each element accounts for 0.01-99.99 at.% of the liquid-phase ammonia-related catalyst, wherein at. represents atomic fraction; When the liquid-phase ammonia-related catalyst includes a transition metal element, the proportion of the transition metal element in the liquid-phase ammonia-related catalyst does not exceed 90at.%; wherein the transition metal element includes at least one of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, platinum, and gold.

3. The liquid-phase ammonia-related catalyst according to claim 1, characterized in that One or at least two elements selected from manganese, iron, and ruthenium are selected as the first component; Select one or at least two elements from gallium, indium, tin, lead, bismuth, lanthanum, cerium, and samarium as the second component; The first component and the second component are dissolved in each other in a liquid state to prepare the liquid-phase ammonia-related catalyst.

4. The liquid-phase ammonia-related catalyst according to claim 1, characterized in that One or at least two elements selected from manganese, iron, and ruthenium are selected as the first component; Select one or at least two elements from gallium, indium, tin, lead, bismuth, lanthanum, cerium, and samarium as the second component; One or at least two elements are selected from lithium, sodium, potassium, rubidium, cesium, francium, magnesium, and calcium as the third component; or one or at least two elements are selected from lithium, sodium, potassium, rubidium, cesium, and francium as the third component; or one or at least two elements are selected from magnesium and calcium as the third component; The first component, the second component, and the third component are dissolved in each other in a liquid state to prepare the liquid-phase ammonia-related catalyst.

5. The liquid-phase ammonia-related catalyst according to claim 1, characterized in that: The liquid-phase ammonia-related catalyst is in a liquid state in which all material components are mutually soluble, and is prepared by pre-dissolving at room temperature or pre-heating and melting; or Direct heating and melting to liquid state under reaction conditions; or, A source material containing an element selected as a liquid-phase ammonia-related catalyst is mixed with a catalyst carrier and a solvent to obtain a suspension; the suspension is filtered and dried in sequence to obtain a catalyst precursor; the precursor is calcined and subjected to a reduction reaction in a reducing gas atmosphere to obtain a carrier-supported liquid-phase ammonia-related catalyst, wherein the liquid-phase ammonia-related catalyst is in a liquid state under reaction conditions.

6. The liquid-phase ammonia-related catalyst according to claim 1, characterized in that: The liquid-phase ammonia-related catalyst is a droplet-type catalyst when used; wherein, The droplet diameter of the droplet-type catalyst is less than 0.1 mm; The preparation method of the droplet-type catalyst is: Atomizing the liquid-phase ammonia-related catalyst into a droplet-type catalyst by any one of pressurization, dual-flow atomization, ultrasound, and centrifugation; or, The liquid-phase ammonia-related catalyst is made into ultrafine powder by any one of liquid atomization followed by rapid cooling, electron beam rapid cooling and quenching, laser surface melting, and mechanical crushing, and the ultrafine powder is placed in a container and heated to form a droplet-type catalyst; or, Loading the components of the liquid-phase ammonia-related catalyst on a carrier, and melting the components on the carrier by heating to form a droplet-type catalyst; or The liquid-phase ammonia-related catalyst is heated, evaporated, and then condensed to form liquid droplets that reflux, thereby obtaining a droplet-type catalyst.

7. An application of a liquid-phase ammonia-related catalyst, characterized in that: The liquid-phase ammonia-related catalyst according to any one of claims 1 to 6 is applied to an ammonia decomposition reaction, an ammonia synthesis reaction, or an SCR denitration reaction.

8. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to an ammonia decomposition reaction, comprising the following steps: Under the condition of reaction temperature of 500-1500°C, the reaction raw material NH3 is introduced into the bottom of the container containing the liquid phase ammonia-related catalyst; The NH3 bubbles float up and come into interfacial contact with the liquid-phase ammonia-related catalyst to generate a catalytic reaction to generate products H2 and N2; The product H2, the product N2 and unreacted NH3 are separated.

9. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to an ammonia decomposition reaction, comprising the following steps: The reaction raw material NH3 is introduced into a container filled with droplets of the liquid-phase ammonia-related catalyst and allowed to remain there for a first preset time, so that the reactant comes into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst, a catalytic reaction occurs, and the product H2 and the product N2 are generated; The product H2, the product N2 and the unreacted NH3 are separated, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from impurities for reuse.

10. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to ammonia synthesis reaction, comprising the following steps: Under the conditions of a reaction temperature of 400-1000°C and a reaction pressure of 0.1-50 MPa, the mixed reaction gas obtained by mixing the reaction raw materials H2 and N2 is introduced into the bottom of the container containing the liquid phase ammonia-related catalyst; The bubbles of the mixed reaction gas float up and come into interfacial contact with the liquid-phase ammonia-related catalyst, causing a catalytic reaction to generate product NH3; The unreacted reaction raw material H2, the unreacted reaction raw material N2 and the product NH3 are separated.

11. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to ammonia synthesis reaction, comprising the following steps: The reaction raw materials H2 and N2 are introduced into a container filled with droplets of the liquid-phase ammonia-related catalyst and allowed to remain there for a predetermined time, so that the reaction raw materials come into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst, a catalytic reaction occurs, and the product NH3 is generated; The product NH3 and the unreacted reaction raw materials H2 and N2 are separated, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from impurities for reuse.

12. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps: Under the condition of reaction temperature of 280-1200°C, the reaction raw materials NH3 and NO-containing reaction raw gas are introduced into the bottom of the container containing the liquid phase ammonia-related catalyst; The bubbles of the reaction raw material NH3 and the reaction raw material gas containing NO float up and come into interfacial contact with the liquid phase ammonia-related catalyst, causing a catalytic reaction. The gaseous products and unreacted products float to the liquid surface and are then treated and discharged to complete the SCR denitration reaction.

13. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps: Passing the reaction raw materials NH3 and the reaction raw material gas containing NO into a container filled with the droplets of the liquid-phase ammonia-related catalyst and holding them for a second preset time, so that the reaction raw materials come into interfacial contact with the droplets of the liquid-phase ammonia-related catalyst and a catalytic reaction occurs; The gaseous products and unreacted gaseous reaction raw materials generated in the catalytic reaction are discharged after treatment, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from impurities before being reused.

14. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The liquid-phase ammonia-related catalyst is applied to the SCR denitration reaction, comprising the following steps: Spraying the reaction raw material NH3 and the droplets of the liquid-phase ammonia-related catalyst into the flue gas containing the NO reaction raw material gas, so that the reaction raw material NH3 and the flue gas containing the NO reaction raw material gas are in interfacial contact with the droplets of the liquid-phase ammonia-related catalyst to cause a catalytic reaction; The gaseous products and unreacted gaseous reaction raw materials produced in the catalytic reaction are discharged after treatment, and the droplets of the liquid-phase ammonia-related catalyst are collected and separated from the impurities and unreacted solid reaction raw materials before being reused.

15. The use of the liquid-phase ammonia-related catalyst according to claim 7, characterized in that: The material components of the liquid-phase ammonia-related catalyst are pre-loaded on the surface of a solid support and introduced into a reaction vessel in solid form. Under reaction conditions, the surface material components of the solid support are heated and melted into droplets, so that the gaseous reactants flow through the solid support and fully contact the droplets on the solid support; The reaction vessel is a fluidized bed reactor, and the liquid-phase ammonia-related catalyst reacts with the gaseous reactants in the fluidized bed in the form of droplets; or The reaction container is a fixed bed reactor, the catalyst supported on the surface of the solid carrier in the form of droplets is pre-filled in the fixed bed reactor, and the gaseous reactant flows through the fixed bed to undergo a catalytic reaction.

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