Waste tributyl phosphate / kerosene emulsion as well as preparation method and application thereof

Abstract

The invention provides a waste tributyl phosphate / kerosene emulsion and 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 provided by the invention comprises the following components: a hydrophilic granular emulsifier, waste tributyl phosphate / kerosene and water, the hydrophilic particle 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. The TBP and DBP in the waste tributyl phosphate / kerosene radioactive organic waste liquid can migrate a water phase and be adsorbed to the surface of the hydrophilic particle emulsifier for in-situ modification, so that the TBP and DBP can be adsorbed to the surface of oil and water, an emulsion system is stabilized, and demulsification and oil-water separation cannot occur for a long time. In addition, hydrogen ions in the oil phase can migrate into the water phase, formation of a weak flocculation structure is promoted, the adsorption capacity of the emulsifier on an oil-water interface is increased, and the stability of the emulsion is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of radioactive organic waste liquid treatment, and in particular relates to a waste tributyl phosphate / kerosene emulsion and a preparation method and application thereof. Background Art

[0002] The reprocessing of spent fuel in the nuclear industry generally adopts the Purex process, which uses tributyl phosphate (TBP) as an extractant and kerosene as a diluent. After long-term use, the performance of the extractant and diluent deteriorates to form radioactive organic waste liquid. This type of radioactive organic waste liquid has a large storage volume and poses safety hazards such as leakage and explosion, and it is in urgent need of treatment. At present, pyrolysis and incineration technology is mostly used to reduce its volume and stabilize it. However, during the treatment process, TBP will pyrolyze to produce phosphoric acid to corrode the container. Usually, particles such as calcium hydroxide or magnesium hydroxide are added as neutralizers to react with phosphoric acid to form phosphates to reduce the adverse effects of pyrolysis products.

[0003] In the pyrolysis incineration process, it is very critical to mix the neutralizer with the waste TBP / kerosene radioactive organic waste liquid to prepare a stable system. Usually, an emulsifier and water are added to it to obtain a stable emulsion system. For example, one technical solution is to use nonylphenol polyoxyethylene ether as an emulsifier to prepare a TBP / kerosene emulsion system with a high TBP content. The emulsification time of the emulsion is <2h, the viscosity is 80.68mPa·s, and the stability time is >20h. However, the above technology ignores the effect of the acidity of the waste TBP / kerosene radioactive organic waste liquid on the stability of the emulsion. There is a certain amount of acidic substances in the waste TBP / kerosene produced by actual distillation, including inorganic acids such as nitric acid and phosphoric acid. At the same time, dibutyl phosphate can also ionize hydrogen ions, which will cause the emulsifier to fail and the emulsion stability to decrease. Summary of the invention

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

[0005] In order to achieve the purpose of the present invention, the present invention provides the following technical solutions:

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

[0007] The hydrophilic particulate emulsifier includes one or more of silicon oxide, titanium oxide 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 particle emulsifier is 10:0.025-0.4.

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

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

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

[0012] Preferably, a dispersant is also included;

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

[0014] Preferably, a neutralizing agent is also included;

[0015] The neutralizing agent is alkaline earth metal hydroxide and / or 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] The present invention also provides a method for preparing the waste tributyl phosphate / kerosene emulsion described in the above technical solution, comprising the following steps:

[0020] first mixing a hydrophilic particulate emulsifier and water 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 for a second time to obtain the waste tributyl phosphate / kerosene emulsion.

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

[0023] The second mixing method is stirring and ultrasonic treatment in sequence; the stirring speed is 500-1200rpm, and the time is 10-120min; the ultrasonic treatment is intermittent ultrasonic treatment, the power is 200-600W, the single time is 5-15s, the interval time each time is 5-10s, and the number of cycles is 10-40 times.

[0024] The present invention also provides the use 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 and incineration of tributyl phosphate / kerosene.

[0025] The invention provides a waste tributyl phosphate / kerosene emulsion, comprising the following components: a hydrophilic particle emulsifier, waste tributyl phosphate / kerosene radioactive organic waste liquid and water; the hydrophilic particle emulsifier comprises one or more of silicon oxide, titanium oxide and zinc oxide; H in the waste tributyl phosphate / kerosene radioactive organic waste liquid + The concentration is 0-0.4 mol / L; the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid and the hydrophilic particle emulsifier is 10:0-0.4; the particle size of the hydrophilic particle emulsifier is 10-40 nm. The TBP and dibutyl phosphate in the waste tributyl phosphate / kerosene radioactive organic waste liquid of the present invention can migrate to the water phase, and then adsorb to the surface of the hydrophilic particle emulsifier and modify the emulsifier in situ, so that it can be adsorbed to the oil-water surface, stabilize the water-in-oil (O / W) Pickering emulsion (the oil phase is TBP / kerosene, and the water phase is deionized water), have excellent aggregation stability, and can prevent demulsification and oil-water separation for a long time. In addition, the hydrogen ions in the oil phase will also migrate to the water phase, promote the emulsifier to form a weak flocculated structure, increase the adsorption amount of the emulsifier at the oil-water interface, and further improve the stability of the emulsion. It can be seen from the results of the embodiments of the present invention that the waste tributyl phosphate / kerosene emulsion provided by the present invention has an emulsification time of less than 2h, a viscosity of less than 60mPa·s, and a phase separation time of more than 90d, that is, it has good stability, moderate viscosity, and is easy to transport, meeting the requirements of the pyrolysis incineration process. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0027] Figure 1 The macroscopic images of the waste tributyl phosphate / kerosene emulsion obtained in Examples 1 to 4 and Comparative Example 1 at 1 day and 7 days;

[0028] Figure 2 The microstructure diagram of the waste tributyl phosphate / kerosene emulsion obtained in Examples 1 to 4 at 1 day and 7 days;

[0029] Figure 3 This is a macroscopic picture of the waste tributyl phosphate / kerosene emulsion obtained in Examples 5 to 6 and Comparative Examples 2 to 4 at 1 day;

[0030] Figure 4 The microstructure diagrams of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 to 6 at 1 day and 90 days and the waste tributyl phosphate / kerosene emulsions obtained in Comparative Examples 3 to 4 at 1 day;

[0031] Figure 5 The graphs are the apparent viscosity variation curves of the waste tributyl phosphate / kerosene emulsions obtained in Examples 2 to 4 after being placed for 7 days and the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 to 6 after being placed for 1 day and 90 days as a function of shear rate; wherein (a) is the apparent viscosity variation curve of the waste tributyl phosphate / kerosene emulsions obtained in Examples 2 to 4 after being placed for 7 days as a function of shear rate, and (b) is the apparent viscosity variation curve of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 to 6 after being placed for 1 day and 90 days as a function of shear rate;

[0032] Figure 6 This is a comparison chart of the apparent viscosity of the waste tributyl phosphate / kerosene emulsion obtained in Example 6 after being left for 1 day and 90 days. DETAILED DESCRIPTION

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

[0034] The hydrophilic particulate emulsifier includes one or more of silicon oxide, titanium oxide 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 particle emulsifier is 10:0.025-0.4; and the particle size of the hydrophilic particle emulsifier is 10-40 nm.

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

[0037] In the present invention, the hydrophilic particle emulsifier includes one or more of silicon oxide, titanium oxide and zinc oxide, and in a specific embodiment, it can be silicon oxide; the particle size of the hydrophilic particle emulsifier is 10 to 40 nm, and in a specific embodiment, it can be 12 nm, 15 nm, 20 nm or 30 nm. TBP and dibutyl phosphate in the waste tributyl phosphate / kerosene radioactive organic waste liquid of the present invention can migrate to the water phase, and then adsorb to the surface of the hydrophilic particle emulsifier and perform in-situ modification on it, so that it can be adsorbed to the oil-water surface, stabilize the emulsion system, have excellent aggregation stability, and can prevent demulsification and oil-water separation for a long time. In addition, the hydrogen ions in the oil phase will also migrate to the water phase, promote the emulsifier to form a weak flocculated structure, increase the adsorption amount of the emulsifier at the oil-water interface, and further improve the stability of the emulsion.

[0038] In the present 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 acid; the waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 25-70 vt% tributyl phosphate, in a specific embodiment, it can be 45 vt%, 50 vt% or 60 vt%; the waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 24-75 vt% kerosene, in a specific embodiment, it can be 30 vt%, 50vt% or 65vt%; the waste tributyl phosphate / kerosene radioactive organic waste liquid includes 0-6vt% dibutyl phosphate, and in a specific embodiment, it can be 1.5vt%, 2vt%, 3vt% or 5vt%; the concentration of the inorganic acid in the waste tributyl phosphate / kerosene radioactive organic waste liquid is 0-0.15mol / L, and in a specific embodiment, it can be 0.06mol / L, 0.08mol / L or 0.12mol / L; the inorganic acid is phosphoric acid and / or nitric acid, and in a specific embodiment, it can be phosphoric acid.

[0039] In the present invention, the waste tributyl phosphate / kerosene emulsion further comprises 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 the present invention, the neutralizer particles in the water phase will aggregate, resulting in reduced emulsion stability, and the added dispersant can be adsorbed onto the particle surface to promote the dispersion of the neutralizer particles in the water phase.

[0040] In the present invention, the waste tributyl phosphate / kerosene emulsion also includes a neutralizer; the neutralizer is an alkaline earth metal hydroxide and / or an alkaline earth metal oxide. In a specific embodiment, the alkaline earth metal hydroxide may be calcium hydroxide or magnesium hydroxide; the alkaline earth metal oxide may be calcium oxide or magnesium oxide; the particle size of the neutralizer is 1 to 10 μm, and in a specific embodiment, may be 3 μm, 5 μm or 7 μm.

[0041] In the present invention, when the waste tributyl phosphate / kerosene emulsion includes a neutralizer, the ratio of the molar amount of calcium or magnesium element to the molar amount of phosphorus element 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 the present invention, the water is deionized water.

[0043] In the present 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 the present invention, the water accounts for 20-60% of the mass of the waste tributyl phosphate / kerosene emulsion, and in a specific embodiment, it can be 40% or 50%.

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

[0046] first mixing a hydrophilic particulate emulsifier and water 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 for a second time to obtain the waste tributyl phosphate / kerosene emulsion.

[0048] In the present invention, the hydrophilic particle emulsifier and water are first mixed to obtain an aqueous suspension of the hydrophilic particle emulsifier. When the waste tributyl phosphate / kerosene emulsion of the present invention further includes a dispersant, in a specific embodiment, the hydrophilic particle emulsifier, the dispersant and water are first mixed to obtain an aqueous suspension of the hydrophilic particle emulsifier.

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

[0050] After obtaining the aqueous suspension of the hydrophilic particle emulsifier, the present invention performs a second mixing of the aqueous suspension of the hydrophilic particle emulsifier and the 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 further includes a neutralizer, the system obtained after the second mixing and the neutralizer are thirdly mixed to obtain the waste tributyl phosphate / kerosene emulsion.

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

[0052] In the present invention, the conditions of the third mixing and the second mixing are the same and will not be described in detail herein.

[0053] The present invention also provides the use 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 and incineration of tributyl phosphate / kerosene.

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

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

[0056] Example 1

[0057] 0.0125 g of silicon oxide particles with a particle size of 12 nm were mixed with 5 g of deionized water, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0059] Example 2

[0060] 0.025 g of silicon oxide particles with a particle size of 12 nm were mixed with 5 g of deionized water, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0062] Example 3

[0063] 0.05 g of silicon oxide particles with a particle size of 12 nm were mixed with 5 g of deionized water, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0065] Example 4

[0066] 0.1 g of silicon oxide particles with a particle size of 12 nm were mixed with 5 g of deionized water, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0068] Example 5

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

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

[0071] Example 6

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

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

[0074] Comparative Example 1

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

[0076] Comparative Example 2

[0077] 0.05 g of silicon oxide particles with a particle size of 12 nm and 5 g of deionized water were mixed, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0079] Comparative Example 3

[0080] 0.05 g of silicon oxide particles with a particle size of 12 nm and 5 g of deionized water were mixed, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0082] Comparative Example 4

[0083] 0.05 g of silicon oxide particles with a particle size of 12 nm and 5 g of deionized water were mixed, and stirred at room temperature and 800 rpm for 30 min to obtain a water suspension of silicon oxide;

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

[0085] Test Case

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

[0087] Figure 1 The macroscopic images of the waste tributyl phosphate / kerosene emulsion obtained in Examples 1 to 4 and Comparative Example 1 at 1d and 7d are shown in FIG. Figure 1 It can be seen that when no nano-silicon oxide particles are added to the system (Comparative Example 1), a stable emulsion cannot be formed, and the oil and water are completely separated after standing for 7 days; when the nano-silicon oxide particles are added in an amount of 0.25% (Example 1), 0.5% (Example 2), 1.0% (Example 3) and 2.0% (Example 4), a stable O / W Pickering emulsion is prepared, no oil phase is precipitated, a small amount of water phase is precipitated, and the amount of water precipitation decreases with the increase of the concentration of nano-silicon oxide particles; after standing for 7 days, the emulsion does not change significantly, indicating that it has long-term stability.

[0088] Figure 2 The microstructure of the waste tributyl phosphate / kerosene emulsion obtained in Examples 1 to 4 at 1d and 7d is shown in FIG. Figure 2It can be seen that the particle size of the waste tributyl phosphate / kerosene emulsion decreases with the increase of the amount of nano-silicon oxide particles added; after being placed for 7 days, the particle size of the emulsion has not changed significantly, further indicating that the system has long-term stability.

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

[0090] Figure 3 This is a macroscopic picture of the waste tributyl phosphate / kerosene emulsion obtained in Examples 5 to 6 and Comparative Examples 2 to 4 at 1 day. Figure 3 It can be seen that after adding magnesium hydroxide particles to the emulsion, when the acidic component in the oil phase (acidic waste TBP / kerosene) is 0.1 mol / L phosphoric acid (Comparative Example 2), the emulsion precipitates a large amount of oil phase, which may be due to the aggregation of magnesium hydroxide particles in the water phase causing the system to be unstable; when the acidic component is 4vt% DBP (Comparative Example 3), the emulsion is relatively stable and no oil phase is precipitated after being placed for 1 day; when the acidic component is 2vt% DBP and 0.06mol / L phosphoric acid (Comparative Example 4), the emulsion system quickly precipitates an oil phase. In order to improve the stability of the emulsion system with both DBP and phosphoric acid, a dispersant fatty alcohol polyoxyethylene ether carboxylic acid (Example 5) or fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid (Example 6) is added, and the system does not precipitate an oil phase after being placed for 1 day.

[0091] Figure 4 The microstructure diagrams of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 to 6 at 1 day and 90 days and the waste tributyl phosphate / kerosene emulsions obtained in Comparative Examples 3 to 4 at 1 day are shown in FIG. Figure 4 The results show that when the acidic component in the oil phase (acidic waste TBP / kerosene) is 4vt% DBP (Comparative Example 3), the emulsion particle size is small and the magnesium hydroxide particles are weakly aggregated. When the acidic component in the oil phase (acidic waste TBP / kerosene) is 2vt% DBP and 0.06mol / L phosphoric acid (Comparative Example 4), the emulsion particle size is larger and the magnesium hydroxide particles form 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 decreases, the number of emulsion droplets increases, and the aggregates of magnesium hydroxide particles become smaller. After the systems of Examples 5 and 6 were left to stand for 90 days, the emulsion particle size did not change significantly, indicating that the addition of a dispersant can promote the dispersion of oil droplets and particles and improve the stability of the emulsion.

[0092] Figure 5The curves of apparent viscosity versus shear rate of the waste tributyl phosphate / kerosene emulsions obtained in Examples 2 to 4 after being placed for 7 days and the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 to 6 after being placed for 1 day and 90 days, wherein (a) is the curve of apparent viscosity versus shear rate of the waste tributyl phosphate / kerosene emulsions obtained in Examples 2 to 4 after being placed for 7 days, and (b) is the curve of apparent viscosity versus shear rate of the waste tributyl phosphate / kerosene emulsions obtained in Examples 5 to 6 after being placed for 1 day and 90 days; Figure 5 As shown in Table 1, the apparent viscosity of all systems decreases with increasing shear rate, indicating that they are non-Newtonian fluids. Moreover, after the emulsion systems in Examples 5 and 6 were left standing for 90 days, the viscosity of the systems did not change significantly. -1 The apparent viscosity of all systems is less than 60 mPa·s, meeting the requirements of engineering applications.

[0093] Figure 6 The following is a comparison of the apparent viscosities of the waste tributyl phosphate / kerosene emulsion obtained in Example 6 after being left for 1 day and 90 days. Figure 6 It can be seen that after adding the neutralizer and the fatty alcohol polyoxypropylene polyoxyethylene ether carboxylic acid as a dispersant, the acidic waste TBP / kerosene emulsion has better stability and appropriate fluidity.

[0094] Table 1 Waste tributyl phosphate / kerosene emulsions obtained in Examples 2 to 6 at 1000s -1 Apparent viscosity data at

[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] From the above examples, it can be seen that the emulsification time of the acid waste TBP / kerosene emulsion system obtained by the emulsifier and emulsification method provided by the present invention is less than 2h, the viscosity is less than 60mPa·s, and the phase separation time is greater than 90d, that is, the stability is good, the viscosity is moderate, and it is easy to transport, which meets the requirements of the pyrolysis incineration process. At the same time, the method provided by the present invention is suitable for the emulsification of acid waste TBP / kerosene organic waste liquid, and the treatment of waste liquid with high TBP content can save treatment costs, and has great economic and environmental benefits.

[0097] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. People can also obtain other embodiments based on this embodiment without creativity, 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 invention comprises the following components: a hydrophilic particle emulsifier, waste tributyl phosphate / kerosene radioactive organic waste liquid and water; The hydrophilic particulate emulsifier includes 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 0-0.4 mol / L; the mass ratio of the waste tributyl phosphate / kerosene radioactive organic waste liquid to the hydrophilic particle emulsifier is 10:0.025-0.4; and the particle size of the hydrophilic particle emulsifier is 10-40 nm.

2. The waste tributyl phosphate / kerosene emulsion according to claim 1, characterized in that: The waste tributyl phosphate / kerosene radioactive organic waste liquid comprises 25-70 vt% tributyl phosphate, 24-75 vt% kerosene, 0-6 vt% dibutyl phosphate and inorganic acid; The concentration of inorganic acid in the waste tributyl phosphate / kerosene radioactive organic waste liquid is 0-0.15 mol / L.

3. The waste tributyl phosphate / kerosene emulsion according to claim 2, characterized in that: The inorganic acid is phosphoric acid and / or nitric acid.

4. The waste tributyl phosphate / kerosene emulsion according to claim 1, characterized in that: Also included are dispersants; The dispersant is a fatty alcohol polyoxyethylene ether compound and a fatty alcohol polyoxypropylene polyoxyethylene ether compound.

5. The waste tributyl phosphate / kerosene emulsion according to claim 1 or 4, characterized in that: Also included are neutralizing agents; The neutralizing agent is alkaline earth metal hydroxide and / or alkaline earth metal oxide.

6. The waste tributyl phosphate / kerosene emulsion according to claim 5, characterized in that: The alkaline earth metal hydroxide is calcium hydroxide or magnesium hydroxide; the alkaline earth metal oxide is calcium oxide or magnesium oxide.

7. The waste tributyl phosphate / kerosene emulsion according to any one of claims 1 to 4, 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.

8. The method for preparing the waste tributyl phosphate / kerosene emulsion according to any one of claims 1 to 7, characterized in that: The following steps are involved: first mixing a hydrophilic particulate emulsifier and water to obtain an aqueous suspension of the hydrophilic particulate emulsifier; The aqueous suspension of the hydrophilic particulate emulsifier and the waste tributyl phosphate / kerosene radioactive organic waste liquid are mixed for a second time to obtain the waste tributyl phosphate / kerosene emulsion.

9. The preparation method according to claim 8, characterized in that: The first mixing method is stirring; the stirring speed is 300 to 1000 rpm, and the time is 10 to 60 minutes; The second mixing method is stirring and ultrasonic treatment in sequence; the stirring speed is 500-1200rpm, and the time is 10-120min; the ultrasonic treatment is intermittent ultrasonic treatment, the power is 200-600W, the single time is 5-15s, the interval time each time is 5-10s, and the number of cycles is 10-40 times.

10. Use of the waste tributyl phosphate / kerosene emulsion according to any one of claims 1 to 7 or the waste tributyl phosphate / kerosene emulsion prepared by the preparation method according to claim 8 or 9 in the pyrolysis and incineration of tributyl phosphate / kerosene.

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