A waste tributyl phosphate / kerosene emulsion, its preparation method and use

Abstract

The application provides a waste tributyl phosphate / kerosene emulsion, a preparation method and application thereof, and belongs to the technical field of low-radioactivity organic waste liquid treatment. The waste tributyl phosphate / kerosene emulsion comprises the following components: a hydrophilic particulate emulsifier, waste tributyl phosphate / kerosene and water; the hydrophilic particulate emulsifier comprises one or more of silicon oxide, titanium oxide and zinc oxide; the concentration of H + in the waste tributyl phosphate / kerosene radioactive organic waste liquid is 0-0.4 mol / L. In the waste tributyl phosphate / kerosene radioactive organic waste liquid, TBP and DBP can migrate to the water phase, are adsorbed to the surface of the hydrophilic particulate emulsifier for in-situ modification, can be adsorbed to the oil-water surface, stabilize the emulsion system, and can not be demulsified and separated into oil and water for a long time. In addition, hydrogen ions in the oil phase migrate to the water phase, promote the formation of a weakly flocculated structure, increase the adsorption amount of the emulsifier at the oil-water interface, and improve the stability of the emulsion.

Description

Technical Field

[0001] This invention belongs to the field of radioactive organic waste liquid treatment technology, specifically relating to a waste tributyl phosphate / kerosene emulsion, its preparation method, and its application. Background Technology

[0002] The reprocessing of spent nuclear fuel commonly employs the Purex process, using tributyl phosphate (TBP) as the extractant and kerosene as the diluent. Over time, the performance of both the extractant and diluent deteriorates, resulting in radioactive organic waste liquid. This type of radioactive organic waste liquid is stored in large quantities, posing safety hazards such as leakage and explosion, and urgently requires treatment. Currently, pyrolysis incineration technology is frequently used for volume reduction and stabilization. However, during the treatment process, TBP pyrolysis produces phosphoric acid that corrodes the containers. Calcium hydroxide or magnesium hydroxide granules are typically added as neutralizing agents, reacting with the phosphoric acid to form phosphates, thus mitigating the adverse effects of the pyrolysis products.

[0003] In the pyrolysis incineration process, it is crucial to prepare a stable system by mixing the neutralizing agent with waste TBP / kerosene radioactive organic waste liquid. This is typically achieved by adding emulsifiers and water to obtain a stable emulsion system. One technical solution utilizes nonylphenol polyoxyethylene ether as an emulsifier to prepare a high-TBP content TBP / kerosene emulsion system with an emulsion formation time of <2 hours, a viscosity of 80.68 mPa·s, and a stabilization time of >20 hours. However, this technique neglects the impact of the acidity of the waste TBP / kerosene radioactive organic waste liquid on emulsion stability. Actual waste TBP / kerosene produced by distillation contains a certain amount of acidic substances, including inorganic acids such as nitric acid and phosphoric acid. Furthermore, dibutyl phosphate can ionize hydrogen ions, leading to emulsifier failure and reduced emulsion stability. Summary of the Invention

[0004] The purpose of this invention is to provide a waste tributyl phosphate / kerosene emulsion, its preparation method, and its application. The waste tributyl phosphate / kerosene emulsion provided by this invention has high stability.

[0005] To achieve the objectives of this invention, the following technical solutions are provided:

[0006] A waste tributyl phosphate / kerosene emulsion comprises the following components: a hydrophilic particulate emulsifier, waste tributyl phosphate / kerosene radioactive organic waste liquid, and water;

[0007] The hydrophilic particulate emulsifier includes one or more of silicon dioxide, titanium dioxide, and zinc oxide;

[0008] The waste tributyl phosphate / kerosene radioactive organic waste liquid contains H +The concentration is 0–0.4 mol / L; the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the hydrophilic particulate emulsifier is 10:0.025–0.4.

[0009] Preferably, the waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 25-70 wt% tributyl phosphate, 24-75 wt% kerosene, 0-6 wt% dibutyl phosphate and inorganic acid;

[0010] The concentration of inorganic acids in waste tributyl phosphate / kerosene radioactive organic waste liquid is 0–0.15 mol / L.

[0011] Preferably, the inorganic acid is phosphoric acid and / or nitric acid.

[0012] Preferably, it also includes a dispersant;

[0013] The dispersant is a fatty alcohol polyoxyethylene ether compound and a fatty alcohol polyoxypropylene polyoxyethylene ether compound.

[0014] Preferably, it also includes a neutralizing agent;

[0015] The neutralizing agent is an alkaline earth metal hydroxide and / or an alkaline earth metal oxide.

[0016] Preferably, the alkaline earth metal hydroxide is calcium hydroxide or magnesium hydroxide; the alkaline earth metal oxide is calcium oxide or magnesium oxide.

[0017] Preferably, the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the dispersant is 10:0 to 0.5;

[0018] The water accounts for 20-60% of the mass of the waste tributyl phosphate / kerosene emulsion.

[0019] This invention also provides a method for preparing the waste tributyl phosphate / kerosene emulsion described in the above technical solution, comprising the following steps:

[0020] The hydrophilic particulate emulsifier and water are mixed to obtain an aqueous suspension of the hydrophilic particulate emulsifier.

[0021] The aqueous suspension of the hydrophilic particulate emulsifier and the waste tributyl phosphate / kerosene radioactive organic waste liquid are mixed to obtain the waste tributyl phosphate / kerosene emulsion.

[0022] Preferably, the first mixing method is stirring; the stirring speed is 300-1000 rpm, and the time is 10-60 min;

[0023] The second mixing method involves sequential stirring and ultrasonic treatment; the stirring speed is 500-1200 rpm, and the time is 10-120 min; the ultrasonic treatment is intermittent ultrasonic treatment with a power of 200-600 W, a single session time of 5-15 s, an interval time of 5-10 s, and a cycle number of 10-40 times.

[0024] The present invention also provides the application of the waste tributyl phosphate / kerosene emulsion described in the above technical solution or the waste tributyl phosphate / kerosene emulsion prepared by the preparation method described in the above technical solution in the pyrolysis incineration of tributyl phosphate / kerosene.

[0025] This invention provides a waste tributyl phosphate / kerosene emulsion, comprising the following components: a hydrophilic particulate emulsifier, waste tributyl phosphate / kerosene radioactive organic waste liquid, and water; the hydrophilic particulate emulsifier comprises one or more of silicon dioxide, titanium dioxide, and zinc oxide; the waste tributyl phosphate / kerosene radioactive organic waste liquid contains H... + The concentration is 0–0.4 mol / L; the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the hydrophilic particulate emulsifier is 10:0–0.4; the particle size of the hydrophilic particulate emulsifier is 10–40 nm. In this invention, TBP and dibutyl phosphate in the waste tributyl phosphate / kerosene radioactive organic waste liquid can migrate into the aqueous phase, and then adsorb onto the surface of the hydrophilic particulate emulsifier, thus modifying the emulsifier in situ. This allows it to adsorb onto the oil-water surface, stabilizing the oil-in-water (O / W) Pickering emulsion (oil phase: TBP / kerosene, aqueous phase: deionized water), exhibiting excellent coalescence stability and preventing demulsification and oil-water separation over a long period. Furthermore, hydrogen ions in the oil phase also migrate into the aqueous phase, promoting the formation of a weakly flocculated structure in the emulsifier, increasing the adsorption amount of the emulsifier at the oil-water interface, and further improving the stability of the emulsion. As can be seen from the results of the embodiments of the present invention, the waste tributyl phosphate / kerosene emulsion provided by the present invention has an emulsification time of <2h, a viscosity of <60mPa·s, and a phase separation time of >90d, that is, good stability, moderate viscosity, and easy transportation, which meets the requirements of pyrolysis incineration process. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 Macroscopic images of the waste tributyl phosphate / kerosene emulsions obtained in Examples 1-4 and Comparative Example 1 at 1 day and 7 days.

[0028] Figure 2 The microstructure diagrams are of the waste tributyl phosphate / kerosene emulsions obtained in Examples 1-4 at 1 day and 7 days.

[0029] Figure 3 Macroscopic images of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 and Comparative Examples 2-4 after 1 day;

[0030] Figure 4 The images show the microstructures of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 and 6 at 1 day and 90 days, and the waste tributyl phosphate / kerosene emulsions obtained in Comparative Examples 3 and 4 at 1 day.

[0031] Figure 5 The graphs show the apparent viscosity of the waste tributyl phosphate / kerosene emulsions obtained in Examples 2-4 after 7 days of storage, and the apparent viscosity of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 after 1 day and 90 days of storage, as a function of shear rate. Among them, (a) is the apparent viscosity of the waste tributyl phosphate / kerosene emulsions obtained in Examples 2-4 after 7 days of storage, and (b) is the apparent viscosity of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 after 1 day and 90 days of storage, as a function of shear rate.

[0032] Figure 6 This is a comparison of the apparent viscosity of the waste tributyl phosphate / kerosene emulsion obtained in Example 6 after 1 day and 90 days. Detailed Implementation

[0033] This invention provides a waste tributyl phosphate / kerosene emulsion, comprising the following components: a hydrophilic particulate emulsifier, waste tributyl phosphate / kerosene radioactive organic waste liquid, and water;

[0034] The hydrophilic particulate emulsifier includes one or more of silicon dioxide, titanium dioxide, and zinc oxide;

[0035] The waste tributyl phosphate / kerosene radioactive organic waste liquid contains H + The concentration is 0–0.4 mol / L; the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the hydrophilic particulate emulsifier is 10:0.025–0.4; the particle size of the hydrophilic particulate emulsifier is 10–40 nm.

[0036] In this invention, unless otherwise specified, all raw materials used in the preparation are preferably commercially available products well known to those skilled in the art.

[0037] In this invention, the hydrophilic particulate emulsifier includes one or more of silicon dioxide, titanium dioxide, and zinc oxide; in a specific embodiment, it can be silicon dioxide. The particle size of the hydrophilic particulate emulsifier is 10–40 nm; in a specific embodiment, it can be 12 nm, 15 nm, 20 nm, or 30 nm. The TBP and dibutyl phosphate in the waste tributyl phosphate / kerosene radioactive organic waste liquid of this invention can migrate to the aqueous phase, and then adsorb onto the surface of the hydrophilic particulate emulsifier, undergoing in-situ modification. This allows it to adsorb onto the oil-water surface, stabilizing the emulsion system and exhibiting excellent coalescence stability, preventing demulsification and oil-water separation over a long period. Furthermore, hydrogen ions in the oil phase also migrate to the aqueous phase, promoting the formation of a weakly flocculated structure in the emulsifier, increasing the adsorption amount of the emulsifier at the oil-water interface, and further improving the stability of the emulsion.

[0038] In this invention, the waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 25-70 vt% tributyl phosphate, 24-75 vt% kerosene, 0-6 vt% dibutyl phosphate (DBP), and inorganic acids; the waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 25-70 vt% tributyl phosphate, which in specific embodiments can be 45 vt%, 50 vt%, or 60 vt%; the waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 24-75 vt% kerosene, which in specific embodiments can be 30 vt%,... The waste tributyl phosphate / kerosene radioactive organic waste liquid contains 0-6 vt% dibutyl phosphate, which in specific embodiments can be 1.5 vt%, 2 vt%, 3 vt%, or 5 vt%. The concentration of inorganic acid in the waste tributyl phosphate / kerosene radioactive organic waste liquid is 0-0.15 mol / L, which in specific embodiments can be 0.06 mol / L, 0.08 mol / L, or 0.12 mol / L. The inorganic acid is phosphoric acid and / or nitric acid, which in specific embodiments can be phosphoric acid.

[0039] In this invention, the waste tributyl phosphate / kerosene emulsion further includes a dispersant; the dispersant is a fatty alcohol polyoxyethylene ether compound and / or a fatty alcohol polyoxypropylene polyoxyethylene ether compound. In a specific embodiment, the fatty alcohol polyoxypropylene polyoxyethylene ether compound is a fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid; the fatty alcohol polyoxyethylene ether compound is a fatty alcohol polyoxyethylene ether carboxylic acid or a fatty alcohol polyoxyethylene ether. In this invention, the neutralizing agent particles in the aqueous phase will aggregate, leading to a decrease in emulsion stability, while the added dispersant can be adsorbed onto the particle surface, promoting the dispersion of the neutralizing agent particles in the aqueous phase.

[0040] In this invention, the waste tributyl phosphate / kerosene emulsion further includes a neutralizing agent; the neutralizing agent is an alkaline earth metal hydroxide and / or an alkaline earth metal oxide. In a specific embodiment, the alkaline earth metal hydroxide can be calcium hydroxide or magnesium hydroxide; the alkaline earth metal oxide can be calcium oxide or magnesium oxide; the particle size of the neutralizing agent is 1-10 μm, and in a specific embodiment, it can be 3 μm, 5 μm or 7 μm.

[0041] In this invention, when the waste tributyl phosphate / kerosene emulsion includes a neutralizing agent, the molar ratio of calcium or magnesium to phosphorus in the waste tributyl phosphate / kerosene emulsion is 1.0 to 1.7:1, more preferably 1.2:1, 1.3:1 or 1.4:1.

[0042] In this invention, the water is deionized water.

[0043] In this invention, the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid, the hydrophilic particulate emulsifier, and the dispersant is 10:0.025-0.4:0-0.5. In specific embodiments, it can be 10:0.05:0.05, 10:0.1:0.1, 10:0.07:0.2, 10:0.2:0.3, or 10:0.3:0.2.

[0044] In this invention, the water accounts for 20-60% of the mass of the waste tributyl phosphate / kerosene emulsion, and in specific embodiments, it can be 40% or 50%.

[0045] This invention also provides a method for preparing the waste tributyl phosphate / kerosene emulsion described in the above technical solution, comprising the following steps:

[0046] The hydrophilic particulate emulsifier and water are mixed to obtain an aqueous suspension of the hydrophilic particulate emulsifier.

[0047] The aqueous suspension of the hydrophilic particulate emulsifier and the waste tributyl phosphate / kerosene radioactive organic waste liquid are mixed to obtain the waste tributyl phosphate / kerosene emulsion.

[0048] This invention involves first mixing a hydrophilic particulate emulsifier and water to obtain an aqueous suspension of the hydrophilic particulate emulsifier. In a specific embodiment, when the waste tributyl phosphate / kerosene emulsion of this invention also includes a dispersant, the hydrophilic particulate emulsifier, dispersant, and water are first mixed to obtain an aqueous suspension of the hydrophilic particulate emulsifier.

[0049] In this invention, the first mixing method is stirring; the stirring speed is 300-1000 rpm, and in a specific embodiment, it can be 500 rpm, 600 rpm or 800 rpm; the time is 10-60 min, and in a specific embodiment, it can be 20 min, 30 min or 50 min; the stirring is carried out at room temperature, and in a specific embodiment, it can be 25±5℃.

[0050] After obtaining an aqueous suspension of the hydrophilic particulate emulsifier, the present invention further mixes the aqueous suspension of the hydrophilic particulate emulsifier with waste tributyl phosphate / kerosene radioactive organic waste liquid to obtain the waste tributyl phosphate / kerosene emulsion. When the waste tributyl phosphate / kerosene emulsion of the present invention also includes a neutralizing agent, the system obtained after the second mixing is further mixed with the neutralizing agent to obtain the waste tributyl phosphate / kerosene emulsion.

[0051] In this invention, the second mixing method involves sequential stirring and ultrasonic treatment; the stirring speed is 500–1200 rpm, and in a specific embodiment, it can be 800 rpm or 1000 rpm; the time is 10–120 min, and in a specific embodiment, it can be 20 min, 50 min, or 90 min; the ultrasonic treatment is intermittent ultrasonic treatment with a power of 200–600 W, and in a specific embodiment, it can be 300 W, 400 W, or 500 W; the single session time is 5–15 s, and in a specific embodiment, it can be 8 s or 10 s; the interval between each session is 5–10 s, and in a specific embodiment, it can be 6 s or 8 s; the number of cycles is 10–40, and in a specific embodiment, it can be 15, 20, or 30 times.

[0052] In this invention, the conditions for the third mixing and the second mixing are the same, and will not be repeated here.

[0053] The present invention also provides the application of the waste tributyl phosphate / kerosene emulsion described in the above technical solution or the waste tributyl phosphate / kerosene emulsion prepared by the preparation method described in the above technical solution in the pyrolysis incineration of tributyl phosphate / kerosene.

[0054] In this invention, the waste tributyl phosphate / kerosene emulsion is used for the pretreatment of organic waste liquid before the pyrolysis and incineration of tributyl phosphate / kerosene, including: transporting the waste tributyl phosphate / kerosene emulsion to a pyrolysis and incineration device, and performing high-temperature pyrolysis and incineration in a nitrogen environment to convert the organic waste liquid into an inorganic solid phase.

[0055] To further illustrate the present invention, the waste tributyl phosphate / kerosene emulsion, its preparation method, and its application provided by the present invention will be described in detail below with reference to the accompanying drawings and embodiments, but these should not be construed as limiting the scope of protection of the present invention.

[0056] Example 1

[0057] 0.0125g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0058] The above silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) was mixed at a concentration of 0.2mol / L and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication, to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0059] Example 2

[0060] 0.025g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0061] The above silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) was mixed at a concentration of 0.2mol / L and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication, to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0062] Example 3

[0063] 0.05g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0064] The above silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) was mixed at a concentration of 0.2mol / L and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication, to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0065] Example 4

[0066] 0.1g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0067] The above silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) was mixed at a concentration of 0.2mol / L and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication, to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0068] Example 5

[0069] 0.025g of silica particles with a particle size of 12nm, 0.05g of fatty alcohol polyoxyethylene ether carboxylic acid, and 5g of deionized water were mixed and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0070] The above silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) with a concentration of 0.2mol / L was mixed and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication. Then, 1g of magnesium hydroxide particles with a particle size of 5μm was added and stirred at 1000rpm for 30min to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0071] Example 6

[0072] 0.025g of silica particles with a particle size of 12nm, 0.05g of fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid, and 5g of deionized water were mixed and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0073] The above silica aqueous suspension and H +5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) with a concentration of 0.2mol / L was mixed and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication. Then, 1g of magnesium hydroxide particles with a particle size of 5μm was added and stirred at 1000rpm for 30min to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0074] Comparative Example 1

[0075] Mix 5g of deionized water and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) was mixed at a concentration of 0.2mol / L and stirred at 1000rpm for 30min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication, to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0076] Comparative Example 2

[0077] 0.05g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0078] The above-mentioned nano-silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 40vt% kerosene, and 0.1mol / L phosphoric acid) with a concentration of 0.2mol / L was mixed and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication. Then, 1g of magnesium hydroxide particles with a particle size of 5μm was added and stirred at 1000rpm for 30min to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0079] Comparative Example 3

[0080] 0.05g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0081] The above silica aqueous suspension and H +5g of TBP / kerosene (60vt% TBP, 36vt% kerosene and 4vt% DBP) at a concentration of 0.2mol / L was mixed and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication. Then, 1g of magnesium hydroxide particles with a particle size of 5μm was added and stirred at 1000rpm for 30min to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0082] Comparative Example 4

[0083] 0.05g of silica particles with a particle size of 12nm were mixed with 5g of deionized water and stirred at room temperature and 800rpm for 30min to obtain an aqueous suspension of silica.

[0084] The above silica aqueous suspension and H + 5g of TBP / kerosene (60vt% TBP, 38vt% kerosene and 2vt% DBP, phosphoric acid concentration of 0.06mol / L) with a concentration of 0.2mol / L was mixed and stirred at 1000rpm for 10min at room temperature. Then, it was sonicated 20 times at 400W, with each sonication lasting 5s and an interval of 5s between each sonication. Then, 1g of magnesium hydroxide particles with a particle size of 5μm was added and stirred at 1000rpm for 30min to obtain a waste tributyl phosphate / kerosene emulsion ((O / W)Pickering emulsion).

[0085] Test case

[0086] The effect of nano-silica particles on emulsion stability was tested, and the results are shown below.

[0087] Figure 1 These are macroscopic images of the waste tributyl phosphate / kerosene emulsions obtained in Examples 1-4 and Comparative Example 1 at 1 day and 7 days, respectively. Figure 1 It can be seen that when no nano-silica particles are added to the system (Comparative Example 1), a stable emulsion cannot be formed, and the oil and water completely separate after standing for 7 days. When the amount of nano-silica particles added is 0.25% (Example 1), 0.5% (Example 2), 1.0% (Example 3), and 2.0% (Example 4), a stable O / WPickering emulsion is prepared, with no oil phase precipitated and a small amount of water phase precipitated. The amount of water precipitated decreases as the concentration of nano-silica particles increases. After standing for 7 days, the emulsion does not change significantly, indicating that it has long-term stability.

[0088] Figure 2 These are microstructure diagrams of the waste tributyl phosphate / kerosene emulsions obtained in Examples 1-4 at 1 day and 7 days. Figure 2It can be seen that the particle size of the waste tributyl phosphate / kerosene emulsion decreases with the increase of nano-silica particles; after 7 days of storage, the particle size of the emulsion does not change significantly, further indicating that the system has long-term stability.

[0089] The effects of the neutralizing agent magnesium hydroxide particles and the dispersant on the stability of the emulsion were tested, and the results are shown below:

[0090] Figure 3 These are macroscopic images of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 and Comparative Examples 2-4 after 1 day. Figure 3 It was found that after adding magnesium hydroxide particles to the emulsion, when the acidic component in the oil phase (acidic waste TBP / kerosene) was 0.1 mol / L phosphoric acid (Comparative Example 2), a large amount of oil phase precipitated from the emulsion, possibly because the aggregation of magnesium hydroxide particles in the aqueous phase led to system instability. When the acidic component was 4 vt% DBP (Comparative Example 3), the emulsion was relatively stable, and no oil phase precipitated after standing for 1 day. When the acidic components were 2 vt% DBP and 0.06 mol / L phosphoric acid (Comparative Example 4), the emulsion system rapidly precipitated an oil phase. To improve the stability of the emulsion system containing both DBP and phosphoric acid, the dispersant fatty alcohol polyoxyethylene ether carboxylic acid (Example 5) or fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid (Example 6) was added, and no oil phase precipitated after the system stood for 1 day.

[0091] Figure 4 These are microstructure diagrams of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 at 1 day and 90 days, and the waste tributyl phosphate / kerosene emulsions obtained in Comparative Examples 3-4 at 1 day. Figure 4 The results showed that when the acidic component in the oil phase (acidic waste TBP / kerosene) was 4 vt% DBP (Comparative Example 3), the emulsion particle size was small, and the magnesium hydroxide particles showed weak aggregation. When the acidic component in the oil phase (acidic waste TBP / kerosene) was 2 vt% DBP and 0.06 mol / L phosphoric acid (Comparative Example 4), the emulsion particle size was large, and the magnesium hydroxide particles formed larger aggregates. After adding fatty alcohol polyoxyethylene ether carboxylic acid (Example 5) or fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid (Example 6) to the system, the emulsion particle size decreased, the number of emulsion droplets increased, and the magnesium hydroxide particle aggregates became smaller. After the systems of Examples 5 and 6 were allowed to stand for 90 days, the emulsion particle size did not change significantly, indicating that the addition of dispersant can promote the dispersion of oil droplets and particles and improve the emulsion stability.

[0092] Figure 5The figures show the apparent viscosity as a function of shear rate for the waste tributyl phosphate / kerosene emulsions obtained in Examples 2-4 after 7 days of storage, and for the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 after 1 day and 90 days of storage. (a) shows the apparent viscosity as a function of shear rate for the waste tributyl phosphate / kerosene emulsions obtained in Examples 2-4 after 7 days of storage, and (b) shows the apparent viscosity as a function of shear rate for the waste tributyl phosphate / kerosene emulsions obtained in Examples 5-6 after 1 day and 90 days of storage. Figure 5 As shown in Table 1, the apparent viscosity of all systems gradually decreases with increasing shear rate, indicating they are non-Newtonian fluids. Furthermore, the emulsion systems in Examples 5 and 6 did not show significant viscosity changes after standing for 90 days. At a shear rate of 1000 s⁻¹... -1 At that time, the apparent viscosity of all systems was less than 60 mPa·s, which meets the requirements for engineering applications.

[0093] Figure 6 This is a comparison graph showing the apparent viscosity of the waste tributyl phosphate / kerosene emulsion obtained in Example 6 after 1 day and 90 days of storage. Figure 6 It can be seen that after adding a neutralizing agent and fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid as a dispersant, the acidic waste TBP / kerosene emulsion has good stability and appropriate fluidity.

[0094] Table 1 shows the waste tributyl phosphate / kerosene emulsions obtained in Examples 2-6 within 1000 seconds. -1 Apparent viscosity data at time

[0095] Sample source Apparent viscosity (mPa·s) Example 2 (7d) 13.8 Example 3 (7d) 21.9 Example 4 (7d) 31.0 Example 5 (1d) 30.3 Example 6 (1d) 55.1 Example 5 (90d) 31.4 Example 6 (90d) 38.9

[0096] As can be seen from the above embodiments, the acidic waste TBP / kerosene emulsion system prepared by the emulsifier and emulsification method provided by the present invention has an emulsification time of <2h, a viscosity of less than 60mPa·s, and a phase separation time of >90d, indicating good stability, moderate viscosity, and easy transportation, meeting the requirements of pyrolysis incineration processes. Furthermore, the method provided by the present invention is applicable to the emulsification of acidic waste TBP / kerosene organic waste liquid, treating waste liquid with high TBP content, saving treatment costs, and possessing significant economic and environmental benefits.

[0097] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A waste tributyl phosphate / kerosene emulsion characterized in that, The emulsion comprises the following components: a hydrophilic particulate emulsifier, a waste tributyl phosphate / kerosene radioactive organic waste liquid, and water; The hydrophilic particulate emulsifier comprises one or more of silicon oxide, titanium oxide, and zinc oxide; The waste tributyl phosphate / kerosene radioactive organic waste liquid contains H + The concentration is 0.2–0.4 mol / L; the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the hydrophilic particulate emulsifier is 10:0.025–0.4; the particle size of the hydrophilic particulate emulsifier is 10–40 nm. The waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 25-70 vol% tributyl phosphate, 24-75 vol% kerosene, 1.5-6 vol% dibutyl phosphate, and an inorganic acid; The concentration of the inorganic acid in the waste tributyl phosphate / kerosene radioactive organic waste liquid is 0.06-0.15 mol / L.

2. The waste tributyl phosphate / kerosene emulsion of claim 1 wherein, The inorganic acid is phosphoric acid and / or nitric acid.

3. The waste tributyl phosphate / kerosene emulsion of claim 1 wherein, The emulsion further comprises a dispersant; The dispersant is a fatty alcohol polyoxyethylene ether compound and a fatty alcohol polyoxypropylene polyoxyethylene ether compound.

4. The waste tributyl phosphate / kerosene emulsion of claim 1 or 3 wherein, The emulsion further comprises a neutralizing agent; The neutralizing agent is an alkaline earth metal hydroxide and / or an alkaline earth metal oxide.

5. The waste tributyl phosphate / kerosene emulsion of claim 4 wherein, The alkaline earth metal hydroxide is calcium hydroxide or magnesium hydroxide; the alkaline earth metal oxide is calcium oxide or magnesium oxide.

6. The waste tributyl phosphate / kerosene emulsion according to any one of claims 1 to 3, characterized in that, The mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the dispersant is 10:0-0.5; the water accounts for 20-60% of the mass of the waste tributyl phosphate / kerosene emulsion.

7. A process for the preparation of the waste tributyl phosphate / kerosene emulsion according to any one of claims 1 to 6, characterized in that, The method comprises the following steps: The hydrophilic particulate emulsifier and water are first mixed to obtain a water suspension of the hydrophilic particulate emulsifier; The water suspension of the hydrophilic particulate emulsifier and the waste tributyl phosphate / kerosene radioactive organic waste liquid are second mixed to obtain the waste tributyl phosphate / kerosene emulsion.

8. The preparation method according to claim 7, characterized in that, The first mixing is performed by stirring at a speed of 300-1000 rpm for 10-60 min; The second mixing is performed by stirring and ultrasonic treatment in sequence; the stirring is performed at a speed of 500-1200 rpm for 10-120 min; the ultrasonic treatment is intermittent ultrasonic treatment at a power of 200-600 W for 5-15 s each time, with an interval of 5-10 s between each time, and a cycle number of 10-40.

9. Use of the waste tributyl phosphate / kerosene emulsion of any one of claims 1-6 or prepared by the method of claim 7 or 8 in tributyl phosphate / kerosene pyrolysis incineration.

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