CN111058051A - Normal-temperature normal-pressure electrochemical nitrogen fertilizer production system - Google Patents
Normal-temperature normal-pressure electrochemical nitrogen fertilizer production system Download PDFInfo
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- CN111058051A CN111058051A CN201911424342.5A CN201911424342A CN111058051A CN 111058051 A CN111058051 A CN 111058051A CN 201911424342 A CN201911424342 A CN 201911424342A CN 111058051 A CN111058051 A CN 111058051A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C5/00—Fertilisers containing other nitrates
- C05C5/02—Fertilisers containing other nitrates containing sodium or potassium nitrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
Abstract
The invention provides a synthesis method of nitrate, which comprises the following steps of carrying out electrochemical reaction on nitrogen to obtain the nitrate. The invention utilizes noble metal and alloy nano particles with activation capability to nitrogen molecules, oxygen precipitation reaction is carried out on the surface of the catalyst, stable nitrogen-nitrogen triple bonds are broken to generate nitrogen oxides, and then the nitrogen oxides are dissolved in water to generate nitrite and nitrate radical. The invention adopts a more direct and environment-friendly electrochemical reaction mode, takes nitrogen as a raw material to carry out electrocatalysis synthesis of nitrate, and the method comprehensively considers the comprehensive utilization of the nitrogen with the duty gas volume of 78 percent and renewable resources and synthesizes the nitrate on the surface of the heterogeneous catalyst. Compared with the traditional industrial catalytic synthesis of nitrate, the method is beneficial to relieving the emission of greenhouse gases, is more environment-friendly and is miniaturized in equipment devices.
Description
Technical Field
The invention belongs to the technical field of nitrate preparation, and relates to a nitrate synthesis method, an electrochemical nitrate synthesis device and a nitrogen fertilizer production system, in particular to a method for synthesizing nitrate by electrocatalytic oxidation of nitrogen at normal temperature and normal pressure, an electrochemical nitrate synthesis device and a renewable energy driven electrocatalytic micro nitrogen fertilizer production system.
Background
Nitrate is a generic term for compounds derived from nitric acid, and is generally a generic term for salts composed of metal ions, ammonium ions, and nitrate ions. Common examples include sodium nitrate, potassium nitrate, ammonium nitrate, calcium nitrate, lead nitrate, cerium nitrate, etc. The nitrate has good water solubility, and the solid nitrate can be decomposed to release oxygen and be decomposed into metal oxide, oxygen and nitrogen dioxide when being heated. The properties of nitrates vary greatly with the environment, for example nitrates are strong oxidizers in high temperature or acidic aqueous solutions, but have little oxidizing effect in alkaline or neutral aqueous solutions. Nitrate and metal ions may also be coordinated in a variety of ways, including monodentate, bidentate or tridentate, and the like. Nitrate is closely related to human life, and relates to the fields of agriculture, industry, military affairs and the like. In agriculture, nitrate is used as a nitrogen fertilizer for plants to absorb, nitrogen is not only a main component of amino acid and protein, but also can synthesize chlorophyll to promote photosynthesis and the like; in addition, the method can also be used for preparing black powder, and the enamel industry is used as a fluxing agent and an oxidizing agent, a decoloring agent, a defoaming agent and a clarifying agent of glass products, a quenching agent for metal heat treatment and the like.
Although a large amount of nitrate exists in nature, the main sources of the nitrate are azotobacter and nitrobacteria are formed through azotobacter reaction, the nitrate obtained by the method has low purity and cannot be directly applied to industrial production. The existing industrial mass production of nitrate mainly prepares nitrate by reacting nitric acid with metal, metal oxide or carbonate, and the method is relatively simple and can be continuously used up to now. However, with the increasing concern of the whole society on environmental protection and production safety, the disadvantages of the traditional nitrate preparation method are increasingly revealed, wherein the production work has potential safety hazards due to the need of using the strong corrosive nitric acid; moreover, the preparation of nitric acid needs high temperature (Habor-Bosch + Ostwald process), consumes a large amount of fossil fuel, causes a large amount of greenhouse gas emission, belongs to the heavy pollution industry, and also does not meet the requirements of green chemistry and sustainable development.
Particularly for agriculture, the amount of nitrate is huge, but the industrial production of nitrate belongs to capital-intensive production, equipment is large-sized, production sites are centralized, and the transportation cost and the inventory cost are indirectly increased by being far away from the most main application site, namely farmland.
Therefore, how to find a novel nitrate synthesis mode will effectively solve the above problems, reduce the pollution to the environment and the harm to operators in the nitrate production process, make the production process more environment-friendly, and more convenient in use, especially suitable for farmland application, and has gradually become one of the focuses of extensive attention of researchers with foresight in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for synthesizing nitrate, in particular to a method for synthesizing nitrate by electrocatalytic oxidation of nitrogen at normal temperature and normal pressure, the present invention adopts heterogeneous electrocatalytic reaction to directly synthesize nitrate on the surface of a catalyst, and provides an electrocatalytic micro nitrogen fertilizer production system driven by renewable energy sources, which is helpful for alleviating greenhouse gas emission, is environment-friendly, has miniaturized equipment and convenient use, and has great commercial value and market prospect in the domestic large background of capacity.
The invention provides a synthesis method of nitrate, which comprises the following steps:
nitrate is obtained after the electrochemical reaction of nitrogen.
Preferably, the electrochemical reaction comprises a three-electrode electrochemical reaction system;
the condition of the electrochemical reaction is normal temperature and normal pressure;
the three-electrode electrochemical reaction system comprises a counter electrode, a working electrode, a reference electrode, a diaphragm and electrolyte.
Preferably, the material of the counter electrode comprises carbon and/or platinum;
the working electrode is made of nano gold sol or gold-platinum alloy catalyst;
the reference electrode comprises a mercury/oxidized mercury reference electrode or a mercury/saturated calomel reference electrode;
the nitrate includes a metal nitrate.
Preferably, the membrane comprises a cation exchange membrane or an anion exchange membrane;
the electrolyte comprises one or more of potassium acetate, sodium acetate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate;
the nitrate comprises potassium nitrate and/or sodium nitrate;
the nitrogen comprises a nitrogen-containing gas;
the working electrode further includes a catalyst support.
Preferably, the catalyst support comprises a carbon paper support and/or a carbon plate support;
the potential interval of the electrochemical reaction system is 2.0V-2.2V vs. RHE;
the nitrogen-containing gas comprises air;
the temperature at the normal temperature is 0-50 ℃;
the pressure at normal pressure is 0.1 MPa.
The invention provides a device for electrochemically synthesizing nitrate, which comprises a counter electrode, a working electrode, a reference electrode, a diaphragm, electrolyte, an electrolytic reaction device, a nitrogen gas inlet device and an exhaust device.
Preferably, the electrolyte is placed in an electrolytic reaction device;
the diaphragm is arranged in the electrolytic reaction device to form a cathode area and an anode area;
the working electrode and the reference electrode are arranged in the anode region, and the counter electrode is arranged in the cathode region;
the gas outlet end of the nitrogen gas inlet device is positioned below the liquid level of the electrolyte in the anode area;
and the air inlet end of the exhaust device is positioned above the liquid level of the electrolyte in the anode area.
The invention provides a nitrogen fertilizer production system, which comprises a fixing screw/nut, an anode heating plate, an anode conductive metal plate, a conductive gas circulation plate, a gas inlet, a gas outlet, a working electrode plate, a reference electrode, an anode hollow frame, an ion exchange membrane, a cathode hollow frame, a counter electrode plate, a cathode conductive metal plate, a cathode heating plate, an electrolyte inlet and a liquid fertilizer outlet;
the anode heating plate, the anode conductive metal plate, the conductive gas circulation plate, the working electrode plate, the anode hollow frame, the ion exchange membrane, the cathode hollow frame, the counter electrode plate, the cathode conductive metal plate and the cathode heating plate are sequentially stacked;
the gas inlet and the gas outlet are respectively arranged on the conductive gas circulation plate, and the nitrogen is distributed in the circulation groove of the gas circulation plate;
the reference electrode, the electrolyte inlet and the liquid fertilizer outlet are respectively arranged on the anode hollow frame.
Preferably, one plane of the anode hollow frame, one plane of the ion exchange membrane and one plane of the cathode hollow frame are sequentially stacked;
a working electrode plate is stacked on the other plane of the anode hollow frame;
the working electrode plate is stacked with a conductive gas circulation plate;
the ion exchange membrane, the anode hollow frame and the working electrode plate form an anode region;
an anode conductive metal plate is stacked on the conductive gas circulation plate;
an anode heating plate is stacked on the anode conductive metal plate;
a counter electrode plate is stacked on the other plane of the cathode hollow frame;
a cathode conductive metal plate is stacked on the counter electrode plate;
a cathode heating plate is stacked on the cathode conductive metal plate;
the ion exchange membrane, the cathode hollow frame and the counter electrode plate form a cathode area;
the nitrogen fertilizer production system is a sealed nitrogen fertilizer production system.
Preferably, the nitrogen fertilizer production system further comprises an electric power supply device;
the positive electrode and the negative electrode of the power supply device are respectively connected with the anode conductive metal plate and the cathode conductive metal plate;
the reference electrode is arranged on the frame of the anode hollow frame and is internally arranged in the anode area;
the electrolyte inlet is arranged on the frame of the anode hollow frame;
the liquid fertilizer outlet is arranged on the frame of the anode hollow frame;
the liquid fertilizer outlet is arranged opposite to the electrolyte inlet.
The invention provides a synthesis method of nitrate, which comprises the following steps of carrying out electrochemical reaction on nitrogen to obtain the nitrate. Compared with the prior art, the invention aims at the problems of large energy consumption, serious pollution, high safety risk, large-scale equipment, centralized production site, high transportation cost and the like of the existing nitrate production process, particularly the nitrate production process is far away from farmlands. The invention abandons the original method for directly synthesizing metal and nitric acid, and aims at solving the problems that the prior other reaction modes, such as the photocatalytic reaction using titanium dioxide as a catalyst for preparing nitrate, but the intermittency and the regionality of photocatalysis limit the application of the nitrate. In the invention, a more direct and environment-friendly electrochemical reaction mode is selected from a plurality of chemical reaction modes, nitrogen is used as a raw material for electrocatalytic synthesis of nitrate, the comprehensive utilization of nitrogen with the duty gas volume of 78% is comprehensively considered, and nitrate is synthesized on the surface of the catalyst through heterogeneous electrocatalytic reaction (electric energy can be converted from intermittent renewable energy sources such as wind energy, solar energy and the like). The invention also aims at the problems of poor repeatability, multiple interference factors, instability and difficulty in reproduction of the existing similar electrochemical technical scheme.
The invention utilizes noble metal nano particles with activation capability to nitrogen molecules to generate oxygen precipitation reaction on the surface of the catalyst, break through stable nitrogen-nitrogen triple bonds to generate nitrogen oxide, and then the nitrogen oxide is dissolved in water to generate nitrite and nitrate radical. And conductive carbon materials can be introduced to further improve the conductivity and the electrocatalytic activity. The electrocatalysis process provided by the invention has good stability, can be repeatedly realized, has relatively few influencing factors, and is easy to implementThe existing process is automatic and is applied in a large scale; the electrode and electrolyte required by the reaction can be recycled, the chemical reaction mainly consumes water, and even industrial sewage can be used for secondary utilization, so that the raw material source is wide; at the same time, the process is combined with the utilization of renewable energy (no CO generation)2) Under the large background of domestic capacity, large-scale electric energy storage and renewable energy conversion can be realized, the implementation of the scheme has great commercial value and market prospect, and an alternative scheme is provided for the consumption of intermittent renewable energy. The electrochemical synthesis method provided by the invention can directly convert electric energy into chemical energy, has higher efficiency, is modularized, is closer to a use place, reduces transportation cost, and is more suitable for agricultural application. The invention also provides a nitrogen fertilizer production system.
The experimental result shows that the invention utilizes the noble metal heterogeneous catalyst, takes the ultrapure air as the reactant under the conditions of normal temperature and normal pressure aqueous solution, and the optimal nitrate radical production rate is 0.93 mu g.h-1·cm-2。
Drawings
FIG. 1 is a schematic design diagram of an evaluation device for electrochemical synthesis of nitrate according to the present invention;
FIG. 2 is a schematic diagram of a design scheme of a nitrogen fertilizer production system provided by the invention;
FIG. 3 is an electrolysis current-time curve of constant potential electrolysis for 2 hours with high purity air introduced in example 1 of the present invention;
FIG. 4 is a linear voltammetry scan curve of a carbon paper supported nanogold sol catalyst working electrode in the environment of high-purity air, nitrogen and argon respectively in example 1 of the invention;
FIG. 5 is a comparison of the standard curves for quantitative analysis of nitrate by ion chromatography in example 1;
FIG. 6 is an ion chromatographic curve of an electrolyte after 2 hours of constant potential electrolysis by introducing high-purity air in example 1 of the present invention;
FIG. 7 is an electrolysis current-time curve of constant potential electrolysis for 2 hours in example 2 of the present invention with high purity air introduced and Au-Pt nano alloy as catalyst;
FIG. 8 is an ion chromatographic curve of an electrolyte after 2 hours of constant potential electrolysis by introducing high-purity air in example 2 of the present invention;
FIG. 9 is an electrolytic current-time curve of constant potential electrolysis for 20 hours in comparative example 1 with high purity air and argon gas introduced;
FIG. 10 is a comparison of the standard curves of quantitative analysis using nitrate according to an ultraviolet spectrophotometer in comparative example 1;
FIG. 11 is a graph of UV spectrophotometer measurements of electrolytes after 20 hours of potentiostatic electrolysis for various compositions;
FIG. 12 is a summary of the nitrate formation concentrations in comparative example 1.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs purity requirements that are conventional in the field of analytical purification or bioelectrochemistry.
All the raw materials, sources and abbreviations thereof, of the present invention belong to conventional sources and abbreviations in the art, and are clearly and clearly defined in the field of related uses, and those skilled in the art can obtain the raw materials commercially available or prepared by conventional methods according to the abbreviations and the corresponding uses.
The invention provides a synthesis method of nitrate, which comprises the following steps:
nitrate is obtained after the electrochemical reaction of nitrogen.
The conditions of the electrochemical reaction are not particularly limited in principle, and conventional conditions in the electrochemical reaction known by the skilled in the art can be used, and the skilled in the art can select and adjust the conditions according to actual conditions, electrolysis requirements and product control. The temperature at normal temperature in the invention is preferably 0-50 ℃, more preferably 10-40 ℃, and more preferably 20-30 ℃. The pressure at the normal pressure is preferably 0.1 MPa.
The present invention is not particularly limited in principle to the specific selection of the nitrogen, which may be selected and adjusted by those skilled in the art according to the actual conditions, electrolysis requirements and product control, and the conventional conditions and selection of nitrogen, which are well known to those skilled in the art, preferably includes a nitrogen-containing gas, specifically air, to ensure the electrochemical reaction and further improve the process stability and yield.
The specific kind of nitrate is not particularly limited in the present invention in principle, and may be selected and adjusted by those skilled in the art according to the actual conditions, electrolysis requirements and product control, under the conventional conditions and selection of nitrogen gas well known to those skilled in the art, and the present invention further improves the process stability and yield by ensuring the electrochemical reaction, and the nitrate preferably includes metal nitrate, more preferably potassium nitrate and/or sodium nitrate, and still more preferably potassium nitrate or sodium nitrate.
The selection of the specific system of the electrochemical reaction is not particularly limited in principle by the present invention, and the electrochemical reaction system known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual situation, the electrolysis requirement and the product control. Specifically, the three-electrode electrochemical reaction system of the present invention preferably comprises a counter electrode, a working electrode, a reference electrode, a separator and an electrolyte.
The material of the counter electrode is not particularly limited in principle, and may be selected and adjusted by those skilled in the art according to the actual conditions, electrolysis requirements and product control, and in order to ensure the electrochemical reaction and further improve the process stability and yield, the material of the counter electrode preferably includes carbon and/or platinum, and more preferably carbon or platinum.
The material of the working electrode is not particularly limited in principle, and may be any material known to those skilled in the art as a material of a working electrode that is conventional in electrochemical reactions, and those skilled in the art may select and adjust the material according to actual conditions, electrolysis requirements, and product control.
The present invention is not limited to other materials of the working electrode in principle, and the materials of the working electrode are conventional in electrochemical reaction, which are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual conditions, electrolysis requirements and product control. Specifically, the carrier may be a carbon paper carrier and/or a carbon plate carrier, and may also be a carbon paper carrier or a carbon plate carrier. Namely, the nano gold sol or the gold-platinum alloy catalyst is loaded on a carbon paper carrier or a carbon plate carrier.
The material of the reference electrode is not particularly limited in principle, and may be a material of a reference electrode that is conventional in electrochemical reactions and is well known to those skilled in the art, and those skilled in the art can select and adjust the reference electrode according to actual conditions, electrolysis requirements and product control.
The material of the diaphragm is not particularly limited in the present invention, and may be any material that is commonly used in electrochemical reactions and is well known to those skilled in the art, and those skilled in the art may select and adjust the material according to the actual situation, the electrolysis requirement and the product control.
The electrolyte is selected in principle without any particular limitation, and may be selected and adjusted by those skilled in the art according to actual conditions, electrolysis requirements and product control, and in order to ensure the electrochemical reaction and further improve the process stability and yield, the electrolyte preferably includes one or more of potassium acetate, sodium acetate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate, and more preferably a potassium acetate solution, a sodium acetate solution, a potassium dihydrogen phosphate solution or a dipotassium hydrogen phosphate solution. Specifically, the concentration of the electrolyte solution of the present invention is preferably 0.1M.
The voltage of the three-electrode electrochemical reaction system is not particularly limited in principle, and can be selected and adjusted according to the actual situation, the electrolysis requirement and the product control by the ordinary voltage in the electrochemical reaction well known to a person skilled in the art, in order to ensure the electrochemical reaction and further improve the process stability and the yield, the potential interval of the three-electrode electrochemical reaction system is preferably 2.1-2.3V vs. rhe, i.e. the potential interval of the electrode potential relative to the standard hydrogen electrode is preferably 2.1-2.3V, more preferably 2.12-2.28V, more preferably 2.15-2.25V, more preferably 2.18-2.22V.
The invention utilizes noble metal heterogeneous catalyst, under the conditions of normal temperature and normal pressure of aqueous solution, and by taking ultrapure air as a reactant, the optimal nitrate radical production rate is 0.93 mu g.h-1·cm-2。
The invention also provides an evaluation device for electrochemically synthesizing the nitrate, which comprises a gas generation device, an electrocatalytic reaction device and a nitrate qualitative/quantitative analysis device. The gas generating device comprises an air steel cylinder/nitrogen steel cylinder and an argon steel cylinder; the catalytic reaction device comprises a working electrode, a counter electrode, a reference electrode, a diaphragm, electrolyte, an electrolytic cell, an air inlet and an air outlet; the nitrate qualitative/quantitative analysis device comprises an ion chromatograph and a peristaltic pump.
The selection, proportion and parameters of the components or conditions in the above-mentioned apparatus of the present invention, and the corresponding preferred principles, etc., correspond to the selection, proportion and parameters of the components or conditions in the above-mentioned synthesis method, and the corresponding preferred principles, etc., if not specifically noted, and are not described in detail herein.
In the invention, the device for electrochemically synthesizing nitrate comprises a counter electrode, a working electrode, a reference electrode, a diaphragm, electrolyte, an electrolytic reaction device, a nitrogen gas inlet device and an exhaust device. The device for electrochemically synthesizing the nitrate is a three-electrode electrochemical reaction system, and corresponding electrodes are a counter electrode, a working electrode and a reference electrode.
In the present invention, in order to better perform the electrolytic reaction, the electrolyte is placed in an electrolytic reaction device, the separator is preferably disposed in the electrolytic reaction device to form a cathode region and an anode region, the working electrode and the reference electrode are preferably disposed in the anode region, and the counter electrode is preferably disposed in the cathode region. In other embodiments, the above-mentioned conventional arrangement may not be adopted, so as to be preferable for the electrochemical reaction.
In the invention, the device for electrochemically synthesizing the nitrate comprises a gas inlet device. The specific location of the gas inlet device is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control.
In the invention, the device for electrochemically synthesizing the nitrate comprises an exhaust device. The specific location of the exhaust device is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control.
Referring to fig. 1, fig. 1 is a schematic design diagram of an evaluation device for electrochemical synthesis of nitrate according to the present invention.
The device comprises a nitrogen gas steel cylinder 1, an argon gas steel cylinder 2, a gas pressure meter 3, a gas pipeline 4, a flowmeter 5, a cathode pool and electrolyte 6, a counter electrode 7, a potentiostat 8, an ion exchange membrane 9, a working electrode 10, a reference electrode 11, an anode pool and electrolyte 12, an air inlet 13, an exhaust port 14, a rubber tube 15, a peristaltic pump 16 and an ion chromatograph 17.
The invention also provides a nitrogen fertilizer production system, which comprises a fixing screw/nut, an anode heating plate, an anode conductive metal plate, a conductive gas circulation plate, a gas inlet, a gas outlet, a working electrode plate, a reference electrode, an anode hollow frame, an ion exchange membrane, a cathode hollow frame, a counter electrode plate, a cathode conductive metal plate, a cathode heating plate, an electrolyte inlet and a liquid fertilizer outlet;
in the invention, the nitrogen fertilizer production system comprises an anode heating plate, an anode conductive metal plate, a conductive gas circulation plate, a working electrode plate, an anode hollow frame, an ion exchange membrane, a cathode hollow frame, a counter electrode plate, a cathode conductive metal plate and a cathode heating plate, wherein the anode conductive metal plate, the conductive gas circulation plate, the working electrode plate, the anode hollow frame, the ion exchange membrane, the cathode hollow frame, the counter electrode plate and the cathode conductive metal plate are sequentially stacked. The specific way of the sequential stacking arrangement, i.e. sequential lamination, i.e. one layer on top of another, is not particularly limited in principle, and can be selected and adjusted by the skilled person according to the actual conditions, the electrolysis requirements and the process control.
The gas inlet and the gas outlet are arranged on the conductive gas circulation plate, and the gas is distributed in the circulation groove of the circulation plate;
the reference electrode, the electrolyte inlet and the liquid fertilizer outlet are respectively arranged on the anode hollow frame;
the selection, proportion and parameters of the components or conditions in the production system of the present invention, and the corresponding preferred principles, etc., may correspond to the selection, proportion and parameters of the components or conditions in the synthesis method or synthesis apparatus, and the corresponding preferred principles, etc., if not specifically noted, and are not described in detail herein.
Specifically, when the nitrogen fertilizer production system is described in the middle area of the structure, the anode hollow frame, the ion exchange membrane and the cathode hollow frame are preferably sequentially stacked, and the working electrode plate is stacked on the other plane of the anode hollow frame.
The internal structure formed after the sequential stacking is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control. Namely, the ion exchange membrane and the working electrode plate (anode catalyst plate) are taken as two planes of the anode region, and the hollow space of the anode hollow frame forms the anode region.
In the invention, the working electrode plate is also stacked with a conductive gas flow plate, namely, one surface of the working electrode plate is used as a plane of the anode region, and the other surface is stacked with the conductive gas flow plate. The device has the function of facilitating the full and uniform diffusion of nitrogen-containing gases such as air or nitrogen and the like, and better uniform dispersion and contact with the working electrode plate. The conductive gas flow plate of the present invention is preferably a gas flow graphite plate.
In the present invention, an anode conductive metal plate is further stacked on the conductive gas flow plate, that is, one surface of the conductive gas flow plate is in contact (composite) with the working electrode plate, and the other surface is stacked with the anode conductive metal plate. The method has the advantages that the method is convenient for external current to be uniformly conducted on the conductive gas circulation plate and the working electrode, and the electrochemical reaction of the nitrogen fertilizer production system is better promoted. In the present invention, the anode conductive metal plate may further include a tab for facilitating connection to an external power source. The conductive metal plate of the present invention is preferably a copper plate.
The internal structure formed after the sequential stacking is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control. I.e., the ion exchange membrane and the counter electrode plate, as two planes of the cathode region, and the hollow space of the cathode hollow frame forms the cathode region.
In the present invention, the counter electrode plate is further stacked with a cathode conductive metal plate, i.e., one surface of the counter electrode plate serves as a plane of the cathode region, and the other surface is stacked with the cathode conductive metal plate. The method has the advantages that the method is convenient for external current to be uniformly conducted on the counter electrode plate, and the reaction of the nitrogen fertilizer production system is better promoted to be carried out. In the present invention, the cathode conductive metal plate may further include a tab for facilitating connection to an external power source.
In the invention, the structure of the nitrogen fertilizer production system forms a sealed nitrogen fertilizer production system. The sealing according to the invention preferably means that the remaining positions are sealed except for the designated air inlet and outlet.
In the invention, the nitrogen fertilizer production system comprises a reference electrode, and the reference electrode is arranged on the anode hollow frame. In order to ensure the proceeding of the electrochemical reaction and further improve the process stability and yield, the reference electrode is preferably arranged on the frame of the anode hollow frame and is internally arranged in the anode area so as to be convenient for contacting the electrolyte in the anode area, and the electrochemical reaction is favorably carried out as a preferred scheme.
In the invention, the nitrogen fertilizer production system comprises an electrolyte inlet, and the electrolyte inlet is arranged on the anode hollow frame. The specific arrangement position of the electrolyte inlet is not particularly limited in principle, and a person skilled in the art can select and adjust the electrolyte inlet according to actual conditions, electrolysis requirements and process control.
In the invention, the nitrogen fertilizer production system comprises a liquid fertilizer outlet, and the liquid fertilizer outlet is arranged on the anode hollow frame. The specific arrangement position of the liquid fertilizer outlet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control.
The specific arrangement position of the liquid fertilizer outlet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control.
In the invention, the nitrogen fertilizer production system comprises a gas inlet and a gas outlet, and the gas inlet and the gas outlet penetrate through the conductive gas circulation plate and are distributed in the circulation groove of the gas circulation plate. The specific arrangement position of the liquid fertilizer outlet is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual conditions, electrolysis requirements and process control.
In the present invention, the nitrogen fertilizer production system preferably further comprises an electric power supply device. The selection and specific connection relationship of the power supply device are not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to actual conditions, electrolysis requirements and process control. The positive electrode and the negative electrode of the power supply device are preferably respectively connected with the anode conductive metal plate and the cathode conductive metal plate. The power supply means is preferably located at a convenient location for use and operation.
Referring to fig. 2, fig. 2 is a schematic diagram of the design scheme of the nitrogen fertilizer production system provided by the invention.
Wherein, 1 is a fixing nut, 2 is an anode heating plate, 3 is a thermocouple, 4 is a temperature sensor, 5 is an anode conductive metal plate, 6 is a conductive gas circulation plate, 7 is a gas inlet, 8 is a gas outlet, 9 is an anode hollow frame, 10 is a working electrode, 11 is a reference electrode, 12 is a liquid fertilizer outlet, 13 is an electrolyte inlet, 14 is an ion exchange membrane, 15 is a cathode hollow frame, 16 is a counter electrode plate, 17 is a cathode conductive metal plate, 18 is a cathode heating plate, and 19 is a fixing screw.
The invention provides a method for synthesizing nitrate by electrocatalytic oxidation of nitrogen at normal temperature and normal pressure, a device for electrochemically synthesizing nitrate and a renewable energy driven electrocatalytic micro nitrogen fertilizer production system. The invention adopts a more direct and environment-friendly electrochemical reaction mode, adopts nitrogen as a raw material to carry out electrocatalysis synthesis of nitrate, comprehensively considers the comprehensive utilization of nitrogen with the duty gas volume of 78 percent, and synthesizes nitrate on the surface of the catalyst through heterogeneous electrocatalysis reaction (electric energy can be converted from wind energy, solar energy and the like).
The invention utilizes noble metal nano particles with the capability of activating nitrogen molecules to break through stable nitrogen-nitrogen triple bonds to generate nitrogen oxides, the nitrogen oxides are dissolved in water to generate nitrite and nitrate, and the nitrite can be quickly oxidized into nitrate ions at the oxidation potential. In addition, the reaction can be carried out in a suitable potential range. Conductive carbon materials can also be introduced to further improve conductivity. Under the large background of domestic capacity, the implementation of the scheme has great commercial value and market prospect. The electrocatalysis process provided by the invention has good stability, can be repeatedly realized, has relatively few influence factors, and is easy to realize process automation and large-scale application; the electrode and electrolyte required by the reaction can be recycled, the chemical reaction mainly consumes water, and even industrial sewage can be used for secondary utilization, so that the raw material source is wide; at the same time, the process is combined with the utilization of renewable energy (no CO generation)2) The large-scale electric energy storage is realized, and the potential application prospect is shown; the electrochemical synthesis method provided by the invention can directly convert electric energy into chemical energy, has higher efficiency, is modularized, is closer to a use place, reduces transportation cost, and is more suitable for agricultural application.
The experimental result shows that the invention utilizes the noble metal heterogeneous catalyst, takes the ultrapure air as the reactant under the conditions of normal temperature and normal pressure aqueous solution, and the optimal nitrate radical production rate is 0.93 mu g.h-1·cm-2。
To further illustrate the present invention, the following will describe in detail a nitrate synthesis method, an electrochemical nitrate synthesis apparatus and a nitrogen fertilizer production system provided by the present invention with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given only for further illustrating the features and advantages of the present invention, not for limiting the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
By using the device shown in FIG. 1, in the quiltIn the electrolytic cell with Nafion membrane separated into cathode and anode, the working electrode is carbon paper supported nano gold sol catalyst, platinum sheet is auxiliary electrode, mercury/saturated calomel electrode is reference electrode, 0.1M potassium acetate aqueous solution is respectively filled in the anode cell and the cathode cell, high-purity air (V) is firstly introduced into the anode cellNitrogen gas:VOxygen gas7:3) for 30 minutes, and then potentiostatic electrolysis (2.1V, 2.2V and 2.3V vs. rhe) was carried out with continuous introduction of high-purity air for 2 hours, the electrolysis current-time curve being shown in fig. 3.
Referring to FIG. 3, FIG. 3 is a graph showing an electrolysis current-time curve of constant potential electrolysis for 2 hours in example 1 of the present invention in which high purity air is introduced.
As can be seen from fig. 3, when the applied voltage is 2.3V vs. rhe, the high voltage causes strong oxidation of the catalyst and the carbon paper, the stability is deteriorated, the stability of the current curve is poor, and the current is gradually decreased as the electrolysis time is prolonged. The current curve is relatively stable when the applied voltage is 2.1V and 2.2V vs. rhe.
The working electrode of example 1 was used, and high-purity air, nitrogen gas and argon gas were introduced in the same manner as described above to perform a control experiment, and the electrolytic curve is shown in FIG. 4.
Referring to fig. 4, fig. 4 is a plot of linear voltammetry scans of a working electrode of a carbon paper supported nano-gold sol catalyst in an environment of high purity air, nitrogen and argon respectively in example 1 of the present invention.
As can be seen from fig. 4, the higher current density of high purity air > nitrogen > argon may be due to the occurrence of nitrogen oxidation.
The electrolytic product of example 1 of the present invention was detected and the standard curve was quantitatively analyzed by nitrate according to ion chromatography.
Referring to fig. 5, fig. 5 is a comparison of the standard curve for quantitative analysis of nitrate by ion chromatography in example 1.
Wherein, fig. 5 (a) is an ion chromatographic curve of a known concentration of nitrate; (b) nitrate quantitative analysis standard curve for ion chromatography.
The electrolyte (3mL) after 2 hours of electrolysis was subjected to ion chromatography (detection curve shown in FIG. 6).
Referring to FIG. 6, FIG. 6 is an ion chromatographic curve of the electrolyte after 2 hours of constant potential electrolysis by introducing high purity air in example 1 of the present invention.
Wherein no nitrate was detected from argon, and the test results for high purity air and nitrogen are shown in table 1.
Referring to Table 1, Table 1 summarizes the nitrate yield by ion chromatography for the working electrode of example 1 after 2 hours of electrolysis.
TABLE 1
Example 2
By using the device shown in fig. 1, in an electrolytic cell which is divided into a cathode and an anode by a Nafion membrane, a working electrode is a carbon paper-loaded gold-platinum nano-alloy catalyst, a platinum sheet is an auxiliary electrode, a mercury/saturated calomel electrode is a reference electrode, 0.1M potassium acetate aqueous solution is respectively filled in the anode cell and the cathode cell, and high-purity air (V) is firstly introduced into the cathode cellNitrogen gas:VOxygen gas7:3) for 30 minutes, and then carrying out potentiostatic electrolysis under continuous feed for 2 hours. The electrolysis current-time curve is shown in FIG. 7.
Referring to fig. 7, fig. 7 is an electrolysis current-time curve of constant potential electrolysis for 2 hours in example 2 of the present invention with high purity air introduced and gold-platinum nano alloy as catalyst.
The same working electrode was used, and nitrogen and argon were introduced in the same manner as described above for the control test.
The electrolytic product of example 2 of the present invention was detected, and the electrolytic solution (3mL) after 2 hours of electrolysis was subjected to ion chromatography (the detection curve is shown in FIG. 8).
Referring to FIG. 8, FIG. 8 is an ion chromatographic curve of the electrolyte after 2 hours of constant potential electrolysis by introducing high purity air in example 2 of the present invention.
The standard curve was quantitatively analyzed by ion chromatography using nitrate, and the test results are shown in Table 2.
Referring to Table 2, Table 2 summarizes the nitrate yield by ion chromatography for the working electrode of example 2 after 2 hours of electrolysis.
TABLE 2
Comparative example 1
By using the device shown in fig. 1, in an electrolytic cell which is divided into a cathode and an anode by a Nafion membrane, a working electrode and an auxiliary electrode are both metal platinum sheets, a mercury/saturated calomel electrode is a reference electrode, 0.3M potassium sulfate aqueous solution is respectively filled in the anode cell and the cathode cell, and high-purity air (V) is respectively introduced into the anode cell and the cathode cellNitrogen gas:VOxygen gas7:3) and argon for 30 minutes, followed by potentiostatic electrolysis (2.19V vs. rhe) with continuous passage of gas for 20 hours, the current-time curve being shown in fig. 9.
Referring to FIG. 9, FIG. 9 is a graph showing an electrolysis current-time curve of constant potential electrolysis for 20 hours in comparative example 1 in which high purity air and argon gas were introduced.
The electrolytic product of comparative example 1 was examined. Since high concentrations of potassium sulfate electrolyte cannot be detected using ion chromatography, the nitrate concentration test is performed using an ultraviolet spectrophotometer here (standard test curve is shown in fig. 10), the test results are shown in fig. 11, and the test results are summarized in fig. 12. Since argon produces a nitrate concentration > that of high purity air, the metallic platinum sheet does not exhibit nitrogen oxidation properties.
Referring to fig. 10, fig. 10 is a comparison of the standard curve of the quantitative analysis using nitrate according to the uv spectrophotometer in comparative example 1.
Wherein, in FIG. 10 (a) is a UV spectrophotometer curve for known concentrations of nitrate; FIG. 10 (b) UV spectrophotometer using nitrate quantitative analysis standard curve.
Referring to fig. 11, fig. 11 is a graph of uv spectrophotometer test curves of electrolytes after 20 hours of potentiostatic electrolysis for various compositions.
Referring to fig. 12, fig. 12 is a summary of the nitrate formation concentrations in comparative example 1.
The present invention provides a method for synthesizing nitrate by electrocatalytic oxidation of nitrogen at normal temperature and pressure, an apparatus for electrochemically synthesizing nitrate, and a system for producing a renewable energy-driven electrocatalytic micro nitrogen fertilizer, which are described in detail above, and the present invention is illustrated by using specific examples, but the above description is only provided to help understand the method and the core concept of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any apparatus or system, and implementing any combination of methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for synthesizing nitrate is characterized by comprising the following steps:
nitrate is obtained after the electrochemical reaction of nitrogen.
2. The method of synthesis of claim 1, wherein the electrochemical reaction comprises a three-electrode electrochemical reaction system;
the condition of the electrochemical reaction is normal temperature and normal pressure;
the three-electrode electrochemical reaction system comprises a counter electrode, a working electrode, a reference electrode, a diaphragm and electrolyte.
3. The method of claim 2, wherein the counter electrode comprises carbon and/or platinum;
the working electrode is made of nano gold sol or gold-platinum alloy catalyst;
the reference electrode comprises a mercury/oxidized mercury reference electrode or a mercury/saturated calomel reference electrode;
the nitrate includes a metal nitrate.
4. The method of synthesis of claim 2, wherein the membrane comprises a cation exchange membrane or an anion exchange membrane;
the electrolyte comprises one or more of potassium acetate, sodium acetate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate;
the nitrate comprises potassium nitrate and/or sodium nitrate;
the nitrogen comprises a nitrogen-containing gas;
the working electrode further includes a catalyst support.
5. The synthesis method of claim 4, wherein the catalyst support comprises a carbon paper support and/or a carbon plate support;
the potential interval of the electrochemical reaction system is 2.0V-2.2V vs. RHE;
the nitrogen-containing gas comprises air;
the temperature at the normal temperature is 0-50 ℃;
the pressure at normal pressure is 0.1 MPa.
6. The device for electrochemically synthesizing the nitrate is characterized by comprising a counter electrode, a working electrode, a reference electrode, a diaphragm, electrolyte, an electrolytic reaction device, a nitrogen gas inlet device and an exhaust device.
7. The apparatus of claim 6, wherein the electrolyte is placed in an electrolytic reaction apparatus;
the diaphragm is arranged in the electrolytic reaction device to form a cathode area and an anode area;
the working electrode and the reference electrode are arranged in the anode region, and the counter electrode is arranged in the cathode region;
the gas outlet end of the nitrogen gas inlet device is positioned below the liquid level of the electrolyte in the anode area;
and the air inlet end of the exhaust device is positioned above the liquid level of the electrolyte in the anode area.
8. A nitrogen fertilizer production system is characterized by comprising a fixing screw/nut, an anode heating plate, an anode conductive metal plate, a conductive gas circulation plate, a gas inlet, a gas outlet, a working electrode plate, a reference electrode, an anode hollow frame, an ion exchange membrane, a cathode hollow frame, a counter electrode plate, a cathode conductive metal plate, a cathode heating plate, an electrolyte inlet and a liquid fertilizer outlet;
the anode heating plate, the anode conductive metal plate, the conductive gas circulation plate, the working electrode plate, the anode hollow frame, the ion exchange membrane, the cathode hollow frame, the counter electrode plate, the cathode conductive metal plate and the cathode heating plate are sequentially stacked;
the gas inlet and the gas outlet are respectively arranged on the conductive gas circulation plate, and the nitrogen is distributed in the circulation groove of the gas circulation plate;
the reference electrode, the electrolyte inlet and the liquid fertilizer outlet are respectively arranged on the anode hollow frame.
9. The apparatus of claim 8, wherein one plane of the anode hollow frame, one plane of the ion exchange membrane and one plane of the cathode hollow frame are sequentially stacked;
a working electrode plate is stacked on the other plane of the anode hollow frame;
the working electrode plate is stacked with a conductive gas circulation plate;
the ion exchange membrane, the anode hollow frame and the working electrode plate form an anode region;
an anode conductive metal plate is stacked on the conductive gas circulation plate;
an anode heating plate is stacked on the anode conductive metal plate;
a counter electrode plate is stacked on the other plane of the cathode hollow frame;
a cathode conductive metal plate is stacked on the counter electrode plate;
a cathode heating plate is stacked on the cathode conductive metal plate;
the ion exchange membrane, the cathode hollow frame and the counter electrode plate form a cathode area;
the nitrogen fertilizer production system is a sealed nitrogen fertilizer production system.
10. The apparatus of claim 9, wherein the nitrogen fertilizer production system further comprises an electrical power supply;
the positive electrode and the negative electrode of the power supply device are respectively connected with the anode conductive metal plate and the cathode conductive metal plate;
the reference electrode is arranged on the frame of the anode hollow frame and is internally arranged in the anode area;
the electrolyte inlet is arranged on the frame of the anode hollow frame;
the liquid fertilizer outlet is arranged on the frame of the anode hollow frame;
the liquid fertilizer outlet is arranged opposite to the electrolyte inlet.
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