ABSTRACT

A pyrochemical process is created to overhaul the safety and well-being of plutonium

spent salts interval storage. The feed material comprising of alkali or soluble base earth chlorides

containing different Pu and Am species.To convert actinides to oxides, it is first oxidized. Then,

at that point, the chlorides are eliminated by vacuum distillation which requires temperature from

750 °C to 1100 °C. After a thorough R&D program, full-scale hardware was built to test the

distillation of active salts. Tests with oxidized NaCl/KCl spent salt yield disinfection components

of chlorides greater than 20000. The distilled salt satisfies the radiologic requirements for

disposal as low-level waste. The goal of this paper is to provide inactive research for pure alkali

and alkali earth chlorides salts distillation, the impact of feed material composition on feed

material composition, and a full-scale active test on NaCl/KCl-based spent salts.

Objectives

 To reduce the pressure in the column above the solvent to less than the mixture's vapor

pressure

 To generate a vacuum and cause the elements with lower vapor pressures to evaporate.

Introduction

Distillation is the process of purifying liquids and separating liquid mixtures into their

constituent parts. When a liquid is heated, some molecules gain enough kinetic energy to escape

into the vapor phase, while others simply return to the liquid. Equilibrium is established as

molecules switch back and forth between liquid and vapor. At higher temperatures, more

molecules have enough kinetic energy to escape, resulting in a greater number of molecules in
the vapor phase. Furthermore, the temperature increases as the vapor pressure rises. When the

vapor pressure equals the applied pressure, the liquid begins to boil. Many compounds cannot be

distilled at atmospheric pressure due to their high boiling temperatures. At their normal boiling

points, the compounds decompose. Certain of these materials, however, can be distilled under

reduced pressure because the required temperature to boil the substance can be reduced

significantly. Liquids boil at lower temperatures in a vacuum.

Vacuum distillation necessarily requires the use of specialized equipment to generate.

The Environment Protection Agency (EPA) designed and patented this invention, which has

been useful to laboratories and other commercialization through the federal technology transfer

act. Vacuum distillation is a method for removing heavy and low vapour pressure impurities at

low levels is suited for materials with low boiling and melting points. Under low or high

pressure, vacuum distillation separates the components of a mixture. Vacuum distillation at a

lower boiling point separates compounds from mixtures of higher boiling point chemicals.

Vacuum distillation is used in a variety of fields to separate and recover valuable products.

Plutonium was isolated and produced for the first time in 1941. When slightly oxidized

and exposed to air, the actinide metal appears silvery and develops a yellow tarnish. It is a

chemically reactive element that belongs to the transuranic element class, with the symbol Pu

and atomic number 94. In fact, one of the most important applications for plutonium is energy. It

is the most important transuranium element because plutonium has been used in the production

of nuclear weapons such as atomic bombs as well as in nuclear power plants to generate

electricity. It has also been used in space probes and other space vehicles as a portable energy

source.
 Americium was created for the first time at the University of Chicago late in 1944.

Americium is a silvery-white synthetic radioactive metal that is relatively soft. It is a radioactive

synthetic chemical element with the symbol Am and the atomic number 95. It is frequently used

in smoke alarms, as a portable gamma-ray source in radiography, and to contribute to the

creation of flat glass. However, producing this isotope in usable quantities is incredibly

expensive.

Nuclear vaults hold the spent salts from the synthesis of metallic plutonium. Chlorides

containing various plutonium and americium species dominate these salts, which include

equimolar NaCl/KCl mixtures and CaCl2 mixtures as well as oxychlorides and metal oxides.

Long-term storage of these materials can be difficult due to the presence of reactive metals like

plutonium or alkali, as well as the hygroscopic qualities of chlorides.

Figure 1. Distillation equipment

The Los Alamos National Laboratory's study worked to improve the treatment by

minimizing the amount of plutonium in the products for safety and health. The salt distillation

technique is used to obtain a very lean fraction of plutonium pyrochemical salts (less than 100

ppm plutonium). The plutonium in the pyrochemical wastes is separated into a stable oxide
substance suitable for long-term storage, whereas the chloride content is converted into a mildly

contaminated salt.

Moreover, the processes and findings of the vacuum distillation process development

program are discussed, including the use of inactive studies to determine the effects of the

composition of the feed material and full-scale active testing on NaCl/KCl-based spent salts.

Materials:

Thermometer Receiving flask

Clamp Ice bath

Condenser Vacuum source

Distilling flask Vacuum adapter

Heat source Water inlet

Water outlet
 Figure 2. Vacuum Distillation Set-up

Methods

1.) Safety note: Inspect all glassware that will be used in vacuum distillation for stars, cracks,

or other weaknesses in the glass, as these may allow for implosion when the pressure is

reduced.

2.) A stir bar should be used to prevent bumps. Vacuum distillation cannot be used with

boiling stones because air trapped in the pores of the stones is rapidly removed under

vacuum, preventing the stones from producing bubbles.

3.) While greasing is a personal preference in simple and fractional distillation, all joints

must be greased in vacuum distillation, or the system will leak and fail to achieve a low

pressure

4.) Assemble the apparatus near the vacuum source. When using a water aspirator, ensure

that it functions properly, as some are more functional than others. To test an aspirator,

apply thick vacuum hose to the aspirator's nub, turn on the water, and use your finger to

feel for suction at the hose's end.

 5.) The apparatus should include a Claisen adapter, as solutions in vacuum tend to bump

violently.

6.) Connect thick-walled tubing to the distillation apparatus's vacuum adapter and a vacuum

trap. While depicts a trap suitable for a water aspirator, a more substantial trap cooled

with dry ice and acetone should be used in conjunction with a portable vacuum to prevent

solvent vapors from degrading the oil pump.

7.) Connect the vacuum source to the trap (aspirator or vacuum pump). It is preferable to

avoid bending or straining the tubing as much as possible, as this may result in a system

leak.

8.) Substitute a wood block or laboratory jack for the stirring plate to allow for the heat

source to be lowered once the distillation is complete.

Procedure

1.) Place the compound unto the distilling flask

2.) Turn on the vacuum to the distillation apparatus slowly, and the compound will start

to bubble.

3.) Wait for the bubbling to stop, then turn the heat source on to apply heat.

4.) Note: always start at low temperature and gradually raise the temperature in order to

prevent flash boil.

5.) Use a nomograph to determine the boiling temperature of the compound.

6.) The distillation starts as soon as the vapors raise unto the condenser.
 7.) The vapor will condense back to liquid form and is circulated by the water inlet and

outlet in the condenser.

8.) Observe that the impurities remain at the distilling flask while the distilled compound

goes through the vacuum adopter and then directed to the receiving flask.

9.) Stop the distillation by turning the heat source off and place the flask unto an ice bath

to cool them off.

10.) Wait for the apparatus to reach atmospheric pressure and remove the receiving

flask for the distilled compound to be accessed.

11.) The rest of the apparatus can be disassembled and cleanse.

Discussion

In this experiment, vacuum distillation was used to reduce pressure in order that the

solvent is less than the mixture’s vapor pressure and to allow the elements with lower vapor

pressures to evaporate. The vacuum distillates were examined as vapor transfer between the

vacuum distiller in this experiment. Lessening the pressure below atmospheric leads to lower

temperature needs for evaporation of distillate constituents, lowering the system’s overall heating

requirements. Controlling vaporization was also improved by monitoring the electric power

supplied to the vaporization chamber. These measurements were used to calculate the rate of

distillation after determining how long the distillation took. The effect of temperature on

vaporization at 800°C, the rate of distillation increases as the temperature rises. The distillation

rate appears to be independent of the residual pressure generated by the vacuum system if it is
less than the vapor pressure of NaCl and KCl. These are significant distillation fluxes obtained

via vacuum distillation. Furthermore, the actual distillation rate is determined by the rate of

evaporation at the liquid-vapor (or solid-vapor) interface, as well as the rate of vapor transfer

away from the surface vapor, which is determined by the pressure differential between the

evaporation and condensation surfaces. The temperature in the vaporization chamber or the

residual pressure imposed downstream by the vacuum pump restricts the distillation rate

depending on the values of these parameters.

Table 1: Apparent distillation rates

COMPOUND Vessel Distillation Distillation rate

Pressure rate (g/cm²/h) (g/h) Temperature

(Pa)

NaCL/ KCl 1 1.8 800 800

NaCL/ KCl 1 3.2 1350 850

NaCL/ KCl 1 3.8 1150 800 – 855

KCl 1 3.6 1090 800 – 855

CaCl2 0.1 1.5 460 1000 – 1100

CaCl2/NaCl 0.1 3 880 800 – 1100

Carbonate behavior was examined during vacuum distillation in NaCl/KCl media

containing various concentrations of lanthanide oxides. These findings and observations can be

explained by the alkali-lanthanide oxide forming process between lanthanides and sodium

carbonate.
 Table 2: Mass balance for distillation of NaCl/KCl-based oxidized spent salts (mass of

product/mass of feed)

Residue % Sweep % Distillate % Balance % Observation

26.69 7.85 32.52 67.07 Feed dispersion due to foaming

44.86 0.61 46.41 91.87

18.38 2.84 74.09 95.32

0.00 0.00 99 99 Blank

16.19 2.71 74.42 93.32

Table 3: Concentration of plutonium for distillation of NaCl/KCl based spent salts.

Run Feed Pu Pu residue Sweep Distillate Decontamination

(wt %) Pu (wt %) PuO2 (wt %) Cl (wt %) Pu (wt%) Pu (ppm) factor of chlorides 2
1 19.26 58.87 66.90 0.13 21.96 <8 >2.5E+04
2 22.98 54.23 61.63 0.03 88.05 < 10 >2E+04
3 15.38 80.57 91.56 0.02 7.53 453 3.4E+02
4 0.00 0.00 0.00 - - <6 -
5 12.68 78.52 89.23 - 7.89 <5 >2.5E+04

According to our calculations, the entire amount of plutonium in the residue is

categorized as PuO2-.The decontamination factor is calculated as the ratio of the total amount of

wt.% Pu in the feed salt prior to distillation to the total amount of wt. % Pu in the chloride

distillate.
Conclusion

Under atmospheric pressure and vacuum conditions, plutonium pyrochemical salts

were distillate.Boiling commences when the vapor pressure of a solution equals the external or

applied pressure. This behaviour occurs because a lower vapor pressure is necessary for boiling,

which can be achieved at a lower temperature. It was found that the distillation of the salts was

considerably increased by a reduction in the pressure. Furthermore, it assumed that the

distillation fluxes were used to establish a model equation for vacuum distillation of these salts.

The initial unit operation in this technique is pyro-oxidation in molten salts. The development of

vacuum distillation has taken longer and is still ongoing due to the several hurdles that must be

addressed. A thorough understanding of the salt distillation phenomena was required, and a study

of the feed material composition was beneficial in anticipating several difficulties related to

spent salts distillation. The studies aimed to create a full-scale distillation system capable of

vacuum distilling plutonium salts at temperatures of up to 1200°C. Then to examine the feed

material composition in order to anticipate some concerns with wasted salts distillation. These

tests showed that a complete treatment for NaCl/KCl-based spent salts as possible. This process

generates alkali chlorides waste that meets the radiological requirements for disposal as Low-

Level Waste. Plutonium retention in the equipment appeared to be quite negligible, with no

build-up observed. Nonetheless, this crucial safety feature must be adequately documented, and a

conclusion demands further specific feedback. Future study will concentrate on qualifying

vacuum distillation for the entire composition domain of plutonium spent salts, as well as

characterization of plutonium oxide residues.

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