CN111170416A - Method for removing nitric acid in nitric acid-containing solution - Google Patents
Method for removing nitric acid in nitric acid-containing solution Download PDFInfo
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- CN111170416A CN111170416A CN202010022749.1A CN202010022749A CN111170416A CN 111170416 A CN111170416 A CN 111170416A CN 202010022749 A CN202010022749 A CN 202010022749A CN 111170416 A CN111170416 A CN 111170416A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/166—Nitrites
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of reaction purification, and relates to a method for removing nitric acid in a nitric acid-containing solution. The method sequentially comprises the following steps: (1) adding metal copper, nitrite and/or nitrous acid into a nitric acid-containing solution for reaction; (2) inserting a cathode and an anode into a nitric acid-containing solution for electrolysis so as to enable metal copper to be electrochemically deposited on the cathode; (3) stopping the electrolytic reaction when the concentration of the nitric acid in the nitric acid-containing solution does not reach the standard, and further reacting the nitric acid in the nitric acid-containing solution with metal copper electrochemically deposited on the cathode; or replacing a new cathode to continue the electrolytic reaction, and further reacting the nitric acid in the nitric acid-containing solution with the metal copper electrochemically deposited on the cathode; (4) and (3) repeating the steps (2) and (3) until the concentration of the nitric acid in the nitric acid-containing solution is reduced to a required level. The method of the invention can more thoroughly remove the nitric acid in the nitric acid-containing solution.
Description
Technical Field
The invention belongs to the technical field of reaction purification, and relates to a method for removing nitric acid in a nitric acid-containing solution.
Background
In the chemical and chemical processes performed in the nitric acid system, it is complicated to separate (remove) nitric acid from the system, and electrodialysis, evaporation and concentration, and formic acid (formaldehyde) denitration are generally adopted.
The electrodialysis technology can remove the nitric acid to a level of 0.5mol/L, but in the electrodialysis process, if the original nitric acid solution contains other salt substances, a certain amount of salt exists in the dialyzate, namely, the dialyzed nitric acid still contains salt, and the dialysis needs to use pure water or low-concentration nitric acid.
The nitric acid can be concentrated to about 6mol/L by evaporation concentration, the evaporation temperature of the nitric acid is obviously increased when the concentration of the nitric acid exceeds the concentration, the evaporation rate is slow, the concentration of the nitric acid in condensate is increased, and the purification coefficient of the nitric acid to salt is reduced. It is therefore necessary to reduce the nitrate concentration and at the same time reduce the acidity by reacting the nitrate with a reducing agent. Formic acid or formaldehyde, which can generate carbon dioxide and water, is generally used as a reducing agent. However, the denitration of formic acid or formaldehyde needs to be carried out at a temperature of 80 ℃ or higher, the reaction rate is difficult to control, and the denitration depth can only reach about 1 mol/L.
Moreover, the methods generally have the problems of more secondary waste liquid, incomplete nitric acid removal and the like.
Disclosure of Invention
The invention aims to provide a method for removing nitric acid from a nitric acid-containing solution, so that the nitric acid in the nitric acid-containing solution can be more thoroughly removed.
To achieve this object, in a basic embodiment, the present invention provides a method for removing nitric acid from a nitric acid-containing solution, said method comprising the steps of, in order:
(1) adding metal copper, nitrite and/or nitrous acid into a nitric acid-containing solution for reaction;
(2) inserting a cathode and an anode into a nitric acid-containing solution for electrolysis so as to enable metal copper to be electrochemically deposited on the cathode;
(3) stopping the electrolytic reaction when the concentration of the nitric acid in the nitric acid-containing solution does not reach the standard, and further reacting the nitric acid in the nitric acid-containing solution with metal copper electrochemically deposited on the cathode; or replacing a new cathode to continue the electrolytic reaction, and further reacting the nitric acid in the nitric acid-containing solution with the metal copper electrochemically deposited on the cathode;
(4) and (3) repeating the steps (2) and (3) until the concentration of the nitric acid in the nitric acid-containing solution is reduced to a required level.
The principle of the invention is as follows:
copper metal may react with nitric acid to form nitrogen oxides and water (formula I below), and the introduction of nitrous acid further reduces the concentration of hydrogen ions in the solution.
The copper ions generated as described above may be deposited on the electrode using an electrolytic reaction (e.g., formula II below), and the generated nitric acid continues to participate in the reaction of formula I and is ultimately consumed.
And finally, recovering the copper ions in the solution by adopting an electrochemical deposition method.
The final product of the whole process is gaseous nitrogen oxide and oxygen, and H in the solution containing nitric acid can be removed+The concentration is reduced to 10-7mol/L (in a nitric acid solution system containing uranium and nitrous acid, H)+The concentration may be further reduced). The deacidification depth of the whole process is controlled by controlling the concentration of copper ions to be finally recovered. The lower the copper ion concentration recovered at the end of the above-mentioned whole process, the H remaining in the system at the end+The lower the concentration, the final H of the deacidified solution can be controlled according to the requirements of the subsequent process+And (4) concentration.
In a preferred embodiment, the invention provides a method for removing nitric acid from a nitric acid-containing solution, wherein in the step (1), the concentration of nitrite and/or nitrous acid is 0.00001-0.2 mol/L.
In a preferred embodiment, the invention provides a method for removing nitric acid from a nitric acid-containing solution, wherein in the step (2), the cathode material is copper, and the anode material is graphite or platinum.
In a preferred embodiment, the invention provides a method for removing nitric acid from a nitric acid-containing solution, wherein in the step (2), the electrolytic reaction is a constant-current electrolytic reaction.
In a preferred embodiment, the present invention provides a method for removing nitric acid from a nitric acid-containing solution, wherein the nitric acid-containing solution is a highly radioactive spent liquor.
In a preferred embodiment, the invention provides a method for removing nitric acid from a nitric acid-containing solution, wherein the high-activity waste liquid contains 1-4 mol/L of nitric acid, 0.01-10 mol/L of actinides (such as uranium, plutonium and neptunium) and 1-900mg/L of fissile elements (such as zirconium and ruthenium).
The method for removing the nitric acid from the nitric acid-containing solution has the advantages that the nitric acid in the nitric acid-containing solution can be more thoroughly removed without increasing the volume of the solution and the types and the amount of ions in the solution.
The invention utilizes the reaction of copper and nitrate radical under the mediation of nitrous acid and utilizes the electrochemical deposition technology to realize the regeneration of copper, which is essentially the electrochemical destruction nitric acid process under the participation of copper. The invention utilizes the participation of copper to solve the problem that nitric acid with the concentration less than 3mol/L cannot be electrochemically removed.
The method of the invention can reduce the pH of the nitric acid-containing solution to a level close to 7 and simultaneously greatly reduce the nitrate concentration, thereby creating conditions for developing other chemical operations under lower acidity (even alkaline environment) after the nitric acid-containing solution system finishes the main chemical process.
Detailed Description
The following examples further illustrate specific embodiments of the present invention.
Example 1:
the high-level waste liquid in the post-treatment process of the spent fuel is a complex nitric acid solution containing actinides, and the nitric acid concentration is about 3mol/L generally. In the process of further separating the high-level radioactive waste liquid, the concentration of nitric acid is required to be lower than 1mol/L and even lower to 0.1mol/L by the existing separation means. The simulated high-level radioactive waste liquid (the composition is shown in the following table 1) is treated by the following method to obtain solution with the concentration of nitric acid less than 1mol/L, 0.5mol/L and 0.1 mol/L.
TABLE 1 simulated high level effluent composition
| Name of ion | Concentration of | Name of ion | Concentration of |
| UO2 2+ | 10mg/L | H+ | 3mol/L |
| Zr4+ | 0.1g/L | NO3 - | 3mol/L |
| MoO4 - | |||
| Sr | 0.146g/L | ||
| Ce | 5.6×10-3g/L | ||
| Eu | 1.67×10-2g/L | ||
| Ru | 1.48×10-2g/L |
1. 1000mL of simulated high-level radioactive waste liquid is taken and placed in a place with the length multiplied by the width multiplied by the height multiplied by 200 multiplied by 100mm330g of copper powder (solid copper is much slower in reaction speed) was charged into the stainless steel reactor, and 15 drops of 1mol/L sodium nitrite was added dropwise at a rate of 5 drops/min with stirring at 600 rpm. The system reaction is started, the metal copper powder is dissolved, and gas NO is generated.
2. After the consumption of metallic copper is nearly completed, the solution is inserted with a length of 100X 50mm2The copper net is used as a cathode, a platinum wire with the diameter of 8mm is used as an anode, and constant current electrolysis is carried out under the current of 10-30A, so that copper is deposited on the copper net.
3. And turning off the power supply, stopping electrolysis and enabling the copper deposited on the cathode to continuously react with the solution.
4. And repeating the operations 2 and 3 until the concentration of the nitric acid in the solution is reduced to a set value.
It should be noted that when the acid concentration of the solution is set to be lower than 0.5mol/L, ions with high ionic potential are hydrolyzed and precipitated in the solution; when the acid concentration of the solution is set to be lower than 0.1mol/L, most trivalent rare earth ions and zirconium, ruthenium and other ions can be hydrolyzed.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (6)
1. A method for removing nitric acid from a nitric acid-containing solution is characterized by sequentially comprising the following steps:
(1) adding metal copper, nitrite and/or nitrous acid into a nitric acid-containing solution for reaction;
(2) inserting a cathode and an anode into a nitric acid-containing solution for electrolysis so as to enable metal copper to be electrochemically deposited on the cathode;
(3) stopping the electrolytic reaction when the concentration of the nitric acid in the nitric acid-containing solution does not reach the standard, and further reacting the nitric acid in the nitric acid-containing solution with metal copper electrochemically deposited on the cathode; or replacing a new cathode to continue the electrolytic reaction, and further reacting the nitric acid in the nitric acid-containing solution with the metal copper electrochemically deposited on the cathode;
(4) and (3) repeating the steps (2) and (3) until the concentration of the nitric acid in the nitric acid-containing solution is reduced to a required level.
2. The method of claim 1, wherein: in the step (1), the concentration of the nitrite and/or the nitrous acid is 0.00001-0.2 mol/L.
3. The method of claim 1, wherein: in the step (2), the cathode material is copper, and the anode material is graphite or platinum.
4. The method of claim 1, wherein: in the step (2), the electrolytic reaction is a constant current electrolytic reaction.
5. The method of claim 1, wherein: the nitric acid-containing solution is a high-radioactivity waste liquid.
6. The method of claim 5, wherein: the high-radioactivity waste liquid contains 1-4 mol/L nitric acid, 0.01-10 mol/L actinide and 1-900mg/L fissile elements.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115477287A (en) * | 2022-10-17 | 2022-12-16 | 中核四0四有限公司 | Nitric acid recovery system and method in uranium purification process |
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| US5894077A (en) * | 1996-11-08 | 1999-04-13 | Aea Technology Plc | Radioactive effluent treatment |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115477287A (en) * | 2022-10-17 | 2022-12-16 | 中核四0四有限公司 | Nitric acid recovery system and method in uranium purification process |
| CN115477287B (en) * | 2022-10-17 | 2023-09-26 | 中核四0四有限公司 | Nitric acid recovery system and method in uranium purification process |
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