CN112678939B - Method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid - Google Patents
Method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid Download PDFInfo
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Abstract
The invention discloses a method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid, which comprises the step of contacting a feed liquid to be treated with a catalyst under the heating condition, wherein the hydrazine nitrate and the hydroxylamine nitrate are catalytically decomposed into nitrogen, hydrogen, water, trace nitrogen oxides, ammonium ions and the like, the catalyst is coconut shell activated carbon-silicon oxide serving as a carrier, active components are ruthenium or a compound of ruthenium and platinum, and the mass fraction of the active components in the catalyst is 1-5%. The invention also discloses a preparation method of the catalyst. The catalyst hydrazine nitrate and hydroxylamine nitrate prepared by the method have the advantages of high decomposition activity, strong nitric acid corrosion resistance, long service life, and high efficiency, safety, economy and environmental protection of the waste liquid treatment method.
Description
Technical Field
The invention belongs to the field of nuclear power waste treatment and environmental protection, and particularly relates to a method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid.
Background
Nuclear power is a green low-carbon clean energy, the technology is mature, and the nuclear power is one of the most practical and feasible technical ways for solving the energy problem. However, nuclear power generates a large amount of waste materials with strong radioactivity, namely spent fuel, and the safety problem of the nuclear power is one of the main factors restricting the large-scale popularization and application of the nuclear power. As is well known, the nuclear fuel utilization rate of the current nuclear reactor is not high, spent fuel contains a large amount of unconverted uranium and value-added nuclides, and is an important nuclear element resource bank, nuclear fuel closed circulation routes are mostly adopted in various nuclear power countries including china, and physical and chemical methods are adopted to separate, purify and recycle useful nuclear elements such as uranium, plutonium, neptunium and the like in the spent fuel, and a typical post-processing process such as a PUREX process: firstly, nitric acid is used for dissolving spent fuel rods, and separation and purification of each nuclide are realized by methods such as extraction of tributyl phosphate and n-dodecane and other organic diluents, reduction and back extraction of hydrazine nitrate and/or hydroxylamine nitrate and other reducing agents. A large amount of nitric acid waste liquid containing reducing agents of hydrazine nitrate and hydroxylamine nitrate is generated in the post-treatment process, according to the minimization principle of radioactive waste after spent fuel post-treatment, the acidic waste liquid is evaporated, concentrated, destroyed, decomposed and absorbed in the subsequent flow to realize the recycling of nitric acid, and the evaporated residue is subjected to deep burying treatment after vitrification and solidification. Hydrazine nitrate and hydroxylamine nitrate are known to have strong reducibility, are easily oxidized and explosive substances with high energy content, and in order to avoid explosion hazard in the concentration treatment process of waste liquid, the hydrazine nitrate and the hydroxylamine nitrate need to be destroyed and removed in advance. At present, the method for removing hydrazine nitrate and hydroxylamine nitrate mainly comprises the steps of adding an oxidant such as sodium nitrite or introducing dinitrogen tetroxide gas and the like, and the hydrazine nitrate, the hydroxylamine nitrate and the like can be oxidized into nitrogen, water, nitrogen oxide and other products for removal, and the method has the following defects: the consumption of the oxidant is large, and the cost is high; the reaction is severe, and certain safety risk exists during engineering application; when sodium nitrite is used as an oxidant, new solid waste sodium nitrate which is not easy to treat is generated; the primary utilization of nitrogen dioxide is low and there is a risk of leakage. Aiming at the problems in the waste liquid treatment process, the inventor discloses a method for efficiently, safely, economically and environmentally removing hydrazine nitrate and hydroxylamine nitrate in nitric acid.
Disclosure of Invention
A method for removing hydrazine nitrate and hydroxylamine nitrate from nitric acid comprises heating a feed liquid to be treated, and contacting the feed liquid with a catalyst, wherein the hydrazine nitrate and the hydroxylamine nitrate in the feed liquid to be treated are catalytically decomposed into nitrogen, hydrogen, water, trace nitrogen oxides, ammonium ions and the like.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for removing hydrazine nitrate and hydroxylamine nitrate from nitric acid comprises heating feed liquid to be treated, contacting with catalyst, and performing catalytic decomposition to remove hydrazine nitrate and hydroxylamine nitrate from nitric acid by using fixed bed continuous reaction mode or suspension slurry bed intermittent reaction mode. Hydrazine nitrate and hydroxylamine nitrate are high-activity substances, and under the condition of proper temperature, pressure and flow, the hydrazine nitrate and hydroxylamine nitrate in the waste liquid are efficiently decomposed into gas products such as nitrogen, ammonia, hydrogen, water, nitrogen oxides and the like under the catalytic action of a proper catalyst, so that the aim of elimination is fulfilled, and the reaction equation is as follows:
the carrier of the catalyst is coconut shell activated carbon-silicon oxide, the mass fraction of active components is 1-5%, wherein the mass fraction of the silicon oxide is 1-3%; the active component is a composite of two metals of ruthenium or ruthenium and platinum, and the mass ratio of ruthenium to platinum is 3: 1.
The waste liquid to be treated consists of an aqueous solution which is saturated and balanced by tributyl phosphate and n-dodecane and contains 0.8-1.5 mol/L of nitric acid, 0.05-0.2 mol/L of hydrazine nitrate and 0.2-0.5 mol/L of hydroxylamine nitrate, and the aqueous solution has strong acidity and corrosivity2The specific particle size is 0.40-0.60 g/mL, the strength is not less than 95%, and the particle size is 4-8 meshes of flaky particles or 20-40 meshes of irregular particles. Before the catalyst preparation dipping process is put into operation, the active carbon carrier is scoured by high-speed airflow or water flow to remove the weak part of the particle corner in advance, so as to obtain the catalystThe service life of the catalyst is better. And drying the abraded activated carbon carrier for more than 5 hours at 120 ℃, and determining the volume of the isovolumetric adsorbed water by adopting a water absorption method test.
The continuous reaction mode of the fixed bed is as follows: the reaction temperature is 60-95 ℃, and the liquid hourly space velocity is 2.0-12 h-1After the treatment is finished, the content of hydrazine nitrate in the feed liquid is not higher than 1.0 multiplied by 10-2mol/L and hydroxylamine nitrate not higher than 1.0X 10-2mol/L, the catalyst treatment feed liquid per unit mass can reach 12000 times.
The suspension slurry bed batch reaction mode is as follows: the reaction temperature is 90-95 ℃, the dosage of the catalyst is 5-10% of the volume of the reaction liquid, the reaction time is 10-120 min, and the hydrazine nitrate in the feed liquid after the treatment is not higher than 1.0 multiplied by 10-2mol/L and hydroxylamine nitrate not higher than 1.0X 10-2mol/L, 5000 times of the catalyst treatment feed liquid per unit mass.
The preparation method of the catalyst comprises the following steps:
taking 95 parts by weight of granular coconut shell activated carbon carrier which is subjected to pre-abrasion treatment and dried, adding fresh ammonium chloride solution with the equal volume of 10-20% by mass, soaking overnight, filtering, and drying the filtered activated carbon granules in a vacuum drying oven at 80 ℃ for 4 hours to obtain the pre-soaked ammonium chloride salt activated carbon carrier. Putting the dried pre-soaked ammonium chloride activated carbon carrier particles into a pan of a medical sugar coating machine, and spraying 40 parts by weight of active substance precursor solution in a rotating state, wherein the solution contains 1-5 parts by weight of ruthenium or ruthenium and platinum, and the precursor substance is ruthenium trichloride or ruthenium trichloride and chloroplatinic acid; continuously and rotationally spraying 9.5 parts by weight of alkaline silica gel solution with the pH of 8.5-10.5, wherein the mass fraction of silicon dioxide in the silica gel solution is 10-30%. In the series of operations, firstly, an activated carbon carrier presoaked with ammonium chloride is obtained, then, an active precursor concentrated solution containing precious metal with target loading is atomized into fine particles and uniformly sprayed on the surface of the carrier, and the fine particles are anchored in the surface layer of carrier particles by utilizing the characteristic that the precious metal platinum, ruthenium salt and ammonium chloride form low-water-solubility substances. And then, a thin layer of silica gel is sprayed and deposited on the surface of the particles, so that the active metal is protected, and the loss in the using process is reduced.
The materials are placed in a drying box and dried for 12 hours at the temperature of 120 ℃, then nitrogen is introduced for protection, the materials are roasted for 5 hours at the temperature of 400 ℃ in a tubular furnace, hydrogen is introduced for reduction for 6 hours at the temperature of 300 ℃, the materials are naturally cooled to the room temperature, and the materials are switched into nitrogen.
And finally, directly transferring the reduced and cooled catalyst into deionized water under the condition of not contacting with air, and repeatedly washing until no precipitation reaction is detected in silver nitrate test, thereby obtaining a catalyst finished product.
The invention has the beneficial effects that:
(1) the method adopts a catalytic decomposition mode to remove the hydrazine nitrate and hydroxylamine nitrate dangerous compounds in the nitric acid waste liquid, and compared with the traditional mode of adding the oxidant, the method is cleaner and more environment-friendly, has no potential safety hazard, and has better economical efficiency than the mode of adding the oxidant.
(2) The catalyst prepared by the invention is suitable for treating waste liquid in a fixed bed continuous mode or a reaction kettle intermittent mode, is simple to operate, is flexible and convenient, can be coupled with a subsequent treatment process, and improves the energy efficiency.
(3) The catalyst prepared by the invention has high decomposition activity of hydrazine nitrate and hydroxylamine nitrate, long service life, mild reaction conditions, over 12000 times of treatment material liquid per unit mass of catalyst in a fixed bed mode, and over 5000 times of treatment material liquid per unit mass of catalyst in a suspension slurry bed intermittent reaction mode.
Drawings
FIG. 1 shows the results of measuring the concentration of residual hydroxylamine nitrate in the product of example 1;
FIG. 2 shows the results of detecting the concentration of residual hydrazine nitrate in the product of example 1;
FIG. 3 shows the results of measuring the concentration of residual hydroxylamine nitrate in the product of example 2;
FIG. 4 shows the results of measuring the concentration of residual hydrazine nitrate in the product of example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples, which are not intended to limit the scope of the present invention.
The waste liquid to be treated of the hydrazine nitrate and the hydroxylamine nitrate in the nitric acid can be process waste liquid in a post-treatment plant, or a simulated preparation feed liquid is adopted to prepare an aqueous solution containing 0.8-1.5 mol/L of nitric acid, 0.05-0.2 mol/L of hydrazine nitrate and 0.2-0.5 mol/L of hydroxylamine nitrate;
adding tributyl n-dodecane phosphate (volume ratio is 1:100) solution with the volume of 5% of that of the aqueous solution, fully stirring to mix and disperse the organic phase and the aqueous solution, standing for natural phase separation, wherein the upper layer is an organic phase containing tributyl phosphate and n-dodecane, the lower layer is a balanced and saturated feed liquid to be treated, separating liquid and discharging the lower layer solution for a catalyst performance test, the test is carried out by adopting a fixed bed continuous mode or a batch mode, and residual hydrazine nitrate and hydroxylamine nitrate in the product are measured by adopting a spectrophotometric method.
Example 1
Taking 95g of granular coconut shell activated carbon carrier (4-8 meshes) which is subjected to pre-abrasion treatment and dried, adding 82g of newly prepared ammonium chloride solution with the mass fraction of 18%, soaking overnight, filtering, and drying the filtered activated carbon granules in a vacuum drying oven at 80 ℃ for 4 hours to obtain 104.6g of activated carbon carrier presoaked with ammonium chloride salt. Putting the dry particles of the pre-soaked ammonium chloride activated carbon carrier into a pan of a medical sugar coating machine, and spraying 40g of ruthenium trichloride solution containing 3.0g of metal ruthenium in a rotating state; continuously spraying 9.5g of alkaline silica gel solution with the pH of 8.5 in a rotating way, wherein the mass fraction of silicon dioxide in the silica gel solution is 24%. Placing the materials in a drying box, drying for 12h at 120 ℃, then transferring into a tubular furnace, introducing nitrogen for protection for 80min, raising the temperature to 400 ℃, and roasting for 5h at constant temperature, wherein the nitrogen flow rate is 40L/h; reducing the hydrogen to 300 ℃ and continuing to reduce for 6h at the hydrogen flow rate of 36L/h, naturally cooling the converter to room temperature, and switching to nitrogen. And directly transferring the reduced and cooled catalyst into deionized water, and repeatedly washing until no precipitation reaction is detected in silver nitrate test to obtain 194.6g of the No. 1 catalyst, wherein the water content of the catalyst is 48.5%.
30g (dry weight) of No. 1 catalyst is loaded into a glass transparent reactor with the inner diameter of 45mm, the outer wall of the reactor is tapped to lead the catalyst layer to be tightly filled, the reaction temperature is 90 ℃, feed liquid to be treated is continuously fed in (the feed liquid is sequentially fed from top to bottom according to the feed liquid number in the table 1), the reaction is carried out for 1154h, wherein the feed liquid flow in the first 300h is 3.0mL/min, the pump flow in the 300h-1154h is 6.0mL/min, 8 batches of feed liquid to be continuously treated are accumulated to be 381.9kg, the composition of each batch of feed liquid is shown in the table 1, the residual hydrazine nitrate and hydroxylamine nitrate content in the effluent liquid are respectively sampled and detected in the morning and evening during the operation process of the device, and the results are shown in the attached figures 1 and 2, and the catalyst treatment waste liquid is 12.73kg/g.cat (12730 times). The result shows that the residual concentrations of hydrazine nitrate and hydroxylamine nitrate in the nitric acid after catalytic decomposition treatment are both lower than 0.01mol/L, and the treated nitric acid feed liquid can continue to be safely concentrated and recycled.
TABLE 1 feed solution composition for each batch
Example 2
Taking 95g of granular coconut shell activated carbon carrier (4-8 meshes) which is subjected to pre-abrasion treatment and dried, adding 90g of newly prepared ammonium chloride solution with the mass fraction of 12%, soaking overnight, filtering, and drying the filtered activated carbon granules in a vacuum drying oven at 80 ℃ for 4 hours to obtain 101.8g of activated carbon carrier presoaked with ammonium chloride salt. Putting the dry particles of the pre-soaked ammonium chloride activated carbon carrier into a pan of a medical sugar coating machine, and spraying 40g of mixed solution of ruthenium trichloride and chloroplatinic acid in a rotating state, wherein the solution contains 3.0g of metal ruthenium and 1.0g of metal platinum; continuously spraying 9.5g of alkaline silica gel solution with the pH value of 10.0 in a rotating way, wherein the mass fraction of silicon dioxide in the silica gel solution is 18 percent. Placing the materials in a drying box, drying for 12h at 120 ℃, then transferring into a tubular furnace, introducing nitrogen for protection for 80min, raising the temperature to 400 ℃, and roasting for 5h at constant temperature, wherein the nitrogen flow rate is 40L/h; reducing the temperature of hydrogen to 300 ℃ and continuing reduction for 6h at the hydrogen flow rate of 36L/h, naturally cooling the de-sintering furnace to room temperature, and switching to nitrogen. And (3) directly transferring the reduced and cooled catalyst into deionized water, and repeatedly washing until no precipitation reaction is detected in silver nitrate test to obtain 197.7g of the 2# catalyst, wherein the water content of the catalyst is 49.3%.
And (2) filling 7.5g (dry weight) of No. 2 catalyst into a stainless steel reactor, tapping the outer wall of the reactor to enable the catalyst layer to be tightly filled, introducing feed liquid to be treated at the reaction temperature of 60 ℃ for reaction, wherein the feed liquid has the flow rate of 0.5mL/min, and the feed liquid consists of aqueous solution of 1.0mol/L nitric acid, 0.1mol/L hydrazine nitrate and 0.3mol/L hydroxylamine nitrate, and is saturated and balanced by tributyl n-dodecane phosphate (the volume ratio is 1: 100). The device reacts at 60 ℃ for 1582h, at 65 ℃ for 96h, at 70 ℃ for 72h, at 75 ℃ for 197h, at 85 ℃ for 485h and at 90 ℃ for 398h, the experiment is ended after 2830h of accumulation work, the treated material liquid accumulates to 98.0kg, the contents of residual hydrazine nitrate and hydroxylamine nitrate in the effluent liquid are sampled and detected every day in the running process of the device, the result is shown in attached figures 3 and 4, and the catalyst treatment waste liquid is 13.07kg/g.cat (13070 times). The result shows that the residual concentrations of hydrazine nitrate and hydroxylamine nitrate in the nitric acid after catalytic decomposition treatment are both lower than 0.01mol/L, and the treated nitric acid feed liquid can continue to be safely concentrated and recycled.
Example 3
The preparation operation of the catalyst was the same as that in example 1, except that the particle size of the carrier was 20-40 mesh, the pH of the silica gel solution was 9.0, and 40g of ruthenium-containing solution of ruthenium trichloride was 4.5g, to obtain 196.2g of No. 3 catalyst, the water content of the catalyst was 48.5%, and the water content of the catalyst was 48.7%.
Adding 100mL of prepared reaction feed liquid (the feed liquid composition is 1.0mol/L nitric acid, 0.1mol/L hydrazine nitrate and 0.3mol/L hydroxylamine nitrate aqueous solution, and through the volume ratio of tributyl n-dodecane phosphate of 1:100 saturation balance) into a 250mL three-necked bottle, starting a constant-temperature magnetic stirring water bath kettle to preheat to 95 ℃, adding 5.23g of No. 3 catalyst (dry product) at the stirring speed of 400rpm, timing the reaction, stopping the reaction when no bubbles are generated in the reaction system, recording the reaction time, recovering the catalyst for the next reaction through decompression suction filtration, sampling the reaction liquid, analyzing the content of each component, recycling the catalyst for 265 times, enabling the reaction time for each time to be between 16 and 72 minutes, enabling the concentrations of residual hydroxylamine nitrate and hydrazine nitrate to be between 0 and 0.01mol/L respectively, co-processing the solution to be 26.5L, and enabling the treatment reaction capacity of the catalyst feed liquid to be 5.32kg/g.
Example 4
The preparation operation of the catalyst was the same as that in example 2, except that the particle size of the carrier was 20-40 mesh, 40g of the noble metal precursor solution contained 1.2g of ruthenium, 0.4g of platinum, and the PH of the silica gel solution was 10.5, wherein the mass fraction of silica was 15%, so that 192.2g of # 4 catalyst was obtained, and the water content of the catalyst was 49.0%.
Adding 100mL of prepared reaction feed liquid (the feed liquid composition is 1.0mol/L nitric acid, 0.1mol/L hydrazine nitrate and 0.3mol/L hydroxylamine nitrate aqueous solution in a volume ratio of 1:100 saturated equilibrium with tributyl n-dodecane phosphate) into a 250mL three-necked bottle, starting a constant-temperature magnetic stirring water bath kettle, preheating to 90 ℃, adding 4.86g of 4# catalyst (dry product) at a stirring speed of 400rpm, timing the reaction, stopping the reaction when no bubbles are generated in the reaction system, recording the reaction time, recovering the catalyst for the next reaction by vacuum filtration, sampling the reaction liquid, analyzing the content of each component, recycling the catalyst for 236 times, enabling the reaction time for each time to be 10-120 minutes, enabling the concentrations of residual hydroxylamine nitrate and hydrazine nitrate to be 0-0.01 mol/L respectively, co-treating the solution for 23.6L, and enabling the catalyst treatment reaction capacity to be 5.10kg/g.
Claims (5)
1. A method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid is characterized in that feed liquid to be treated is contacted with a catalyst under the heating condition, the hydrazine nitrate and the hydroxylamine nitrate in the feed liquid to be treated are catalytically decomposed, and the hydrazine nitrate and the hydroxylamine nitrate in the nitric acid are finally removed;
the carrier in the catalyst is coconut shell activated carbon-silicon oxide, wherein the mass fraction of the silicon oxide is 1-3%; the mass fraction of the active component is 1-5%, the active component is a composite of two metals of ruthenium or ruthenium and platinum, and the mass ratio of ruthenium to platinum in the composite is 3: 1;
the material liquid to be treated is an aqueous solution containing 0.8-1.5 mol/L of nitric acid, 0.05-0.2 mol/L of hydrazine nitrate and 0.2-0.5 mol/L of hydroxylamine nitrate;
adopting a fixed bed continuous reaction mode or a suspension slurry bed intermittent reaction mode;
the reaction conditions of the fixed bed continuous reaction mode are as follows: the reaction temperature is 60-95 ℃, and the liquid hourly space velocity is 2.0-12 h-1；
Or, the reaction conditions of the suspension slurry bed batch reaction mode are as follows: the reaction temperature is 90-95 ℃, the dosage of the catalyst is 5-10% of the volume of the reaction liquid, and the reaction time is 10-120 min.
2. The removal method of claim 1, wherein: the feed liquid to be treated is an aqueous solution which is saturated and balanced by tributyl phosphate and n-dodecane and contains 0.8-1.5 mol/L of nitric acid, 0.05-0.2 mol/L of hydrazine nitrate and 0.2-0.5 mol/L of hydroxylamine nitrate;
the saturated equilibrium process of tributyl phosphate and n-dodecane is as follows: adding tributyl phosphate and n-dodecane solution with the volume ratio of 1:100 of the aqueous solution to the aqueous solution, fully stirring to mix and disperse the organic phase and the aqueous solution, standing for natural phase separation, wherein the upper layer is an organic phase containing tributyl phosphate and n-dodecane, the lower layer is a balanced and saturated feed liquid to be treated, and separating the liquid and discharging the lower layer solution.
3. The removal method of claim 1, wherein the catalyst is prepared by a method comprising the steps of:
(1) taking 95 parts by weight of granular coconut shell activated carbon carrier, adding an ammonium chloride solution with the equal volume mass fraction of 10-20%, soaking overnight, filtering, and carrying out vacuum drying treatment on the filtered activated carbon granules;
(2) putting the dried activated carbon particles into a pan body of a medical sugar coating machine, and spraying 40 parts by weight of active substance precursor solution in a rotating state, wherein the solution contains 1-5 parts by weight of ruthenium or ruthenium and platinum, and the precursor substance is ruthenium trichloride or ruthenium trichloride and chloroplatinic acid; continuously and rotatably spraying 9.5 parts by weight of alkaline silica gel solution with the pH value of 8.5-10.5, wherein the mass fraction of silicon dioxide in the silica gel solution is 10-30%;
(3) drying the impregnated material at 120 ℃ for 12h, then introducing nitrogen to protect the material in a tubular furnace at 400 ℃ for roasting for 5h, then continuously introducing hydrogen to reduce the material at 300 ℃ for 6h, naturally cooling the material to room temperature, and switching the material into nitrogen;
(4) and (4) directly transferring the material in the step (3) to deionized water under the condition of not contacting air, namely isolating air, and repeatedly washing until no precipitation reaction is detected in silver nitrate test, thereby obtaining the catalyst.
4. The removal process of claim 1, wherein when employedIn the fixed bed continuous reaction mode: the reaction temperature is 60-95 ℃, and the liquid hourly space velocity is 2.0-12 h-1After the treatment is finished, the content of hydrazine nitrate in the feed liquid is not higher than 1.0 multiplied by 10-2mol/L and hydroxylamine nitrate not higher than 1.0X 10-2mol/L, the catalyst treatment feed liquid per unit mass can reach over 12000 times of the mass.
5. The method for removing hydrazine nitrate and hydroxylamine nitrate in nitric acid according to claim 1, wherein when a suspension slurry bed batch reaction mode is adopted: the reaction temperature is 90-95 ℃, the dosage of the catalyst is 5-10% of the volume of the reaction liquid, the reaction time is 10-120 min, and the hydrazine nitrate in the feed liquid after the treatment is not higher than 1.0 multiplied by 10-2mol/L and hydroxylamine nitrate not higher than 1.0X 10-2mol/L, the catalyst treatment feed liquid per unit mass can reach more than 5000 times of the mass.
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| FR2907346A1 (en) * | 2006-10-23 | 2008-04-25 | Commissariat Energie Atomique | Separating actinide groups in strong acidic aqueous phase, comprises coextraction of actinides, lanthanides or yttrium and optionally few other fission products and extraction of actinides |
| CN102133526A (en) * | 2010-12-23 | 2011-07-27 | 西安凯立化工有限公司 | Method for preparing ruthenium carbon catalyst |
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