#####################################################################################################
# “PrOMMiS” was produced under the DOE Process Optimization and Modeling for Minerals Sustainability
# (“PrOMMiS”) initiative, and is copyright (c) 2023-2026 by the software owners: The Regents of the
# University of California, through Lawrence Berkeley National Laboratory, et al. All rights reserved.
# Please see the files COPYRIGHT.md and LICENSE.md for full copyright and license information.
#####################################################################################################
r"""
Reaction package for solvent extraction of rare earth elements using DEHPA as extractant
with TBP as a phase modifier.
----------------------------------------------------------------------------------------
Author: Arkoprabho Dasgupta
This is an example of how to write a reaction package for rare earth elements involved in
solvent extraction.
"""
from pyomo.common.config import ConfigValue
from pyomo.environ import Constraint, Param, Set, Var, units, log10
from idaes.core import ProcessBlock, ProcessBlockData, declare_process_block_class
from idaes.core.base import property_meta
from idaes.core.util.misc import add_object_reference
from idaes.core.scaling import CustomScalerBase
__author__ = "Arkoprabho Dasgupta, Douglas Allan"
# -----------------------------------------------------------------------------
# Solvent extraction property package
@declare_process_block_class("SolventExtractionReactions")
class SolventExtractionReactionsData(
ProcessBlockData, property_meta.HasPropertyClassMetadata
):
"""
Reaction package for the solvent extraction of rare earth elements from acidic aqueous
solution using organic extractant DEHPA and TBP as phase modifier.
Rare earth elements : La, Pr, Ce, Dy, Nd, Sm, Gd, Y
Impurities : Al, Ca, Fe, Sc
This reaction package is used by the solvent extraction model. It assumes that there are
two streams involved in the mass transfer, the aqueous liquid phase named as 'liquid' in
the package, and the organic phase named as 'organic'.
The material transfer amount is accounted through the term of the heterogeneous reaction
extent term in the solvent extraction model. The amount of material transfer is quantified
through the use of distribution coefficient.
The distribution coefficient is defined as the ratio of the concentration in the organic
phase to the concentration in the aqueous phase.
D[i] = C_organic[i]/C_aqueous[i] i = REEs and Impurities
This reaction package is for a system where DEHPA acts as the main extractant and TBP acts
as the phase modifier in the system.
There are impurities considered in the system. We do not have adequate data points for
the impurities, so their distribution coefficient values has been calculated from REESim file
and assumed constant.
For the rare earth elements, the distribution correlation can be expressed in the following
correlation.
logD[i] = m[i]*pH + B[i] i = REEs
These correlations have been taken from 'PROCESSES RESEARCH PROJECT REPORT Production of
salable rare earths products from coal and coal byproducts using advanced separation processes
Phase 1'.
The parameters for each of the components m[i],B[i] can be expressed as an empirical function
of the extractant dosage (volume percentage) of the system.
m[i] = m0[i] + m1[i]*dosage
B[i] = B0[i] + B1[i]*log(dosage)
The dosage is set by the extractant_dosage variable on the organic state block.
The data points for these empirical correlations have been taken from the phase 1 report.
Certain rare earth elements do not have adequate data, hence certain functionalities could
not be written here.
"""
def build(self):
super().build()
self._reaction_block_class = SolventExtractionReactionsBlock
REE_list = ["La", "Y", "Pr", "Ce", "Nd", "Sm", "Gd", "Dy"]
Impurity_list = ["Al", "Ca", "Fe", "Sc"]
index_list = [f"{e}_mass_transfer" for e in (REE_list + Impurity_list)]
element_list = REE_list + Impurity_list
self.element_list = Set(initialize=element_list)
self.reaction_idx = Set(initialize=index_list)
reaction_stoichiometry = {}
for e in REE_list:
reaction_stoichiometry[(f"{e}_mass_transfer", "liquid", e)] = -1
reaction_stoichiometry[(f"{e}_mass_transfer", "organic", f"{e}_o")] = 1
reaction_stoichiometry[(f"{e}_mass_transfer", "liquid", "H")] = 3
reaction_stoichiometry[(f"{e}_mass_transfer", "organic", "DEHPA")] = -3
for e in Impurity_list:
if e == "Ca":
reaction_stoichiometry[(f"{e}_mass_transfer", "liquid", e)] = -1
reaction_stoichiometry[(f"{e}_mass_transfer", "organic", f"{e}_o")] = 1
reaction_stoichiometry[(f"{e}_mass_transfer", "liquid", "H")] = 2
reaction_stoichiometry[(f"{e}_mass_transfer", "organic", "DEHPA")] = -2
else:
reaction_stoichiometry[(f"{e}_mass_transfer", "liquid", e)] = -1
reaction_stoichiometry[(f"{e}_mass_transfer", "organic", f"{e}_o")] = 1
reaction_stoichiometry[(f"{e}_mass_transfer", "liquid", "H")] = 3
reaction_stoichiometry[(f"{e}_mass_transfer", "organic", "DEHPA")] = -3
self.reaction_stoichiometry = reaction_stoichiometry
self.m0 = Param(
self.element_list,
initialize={
"Ce": 0.30916,
"Y": 1.63166,
"Gd": 1.0225,
"Dy": 1.70783,
"Sm": 0.81233,
"Nd": 0.31183,
"La": 0.54,
"Pr": 0.29,
"Sc": 0,
"Al": 0,
"Ca": 0,
"Fe": 0,
},
)
self.m1 = Param(
self.element_list,
initialize={
"Ce": 0.04816,
"Y": 0.15166,
"Gd": 0.0195,
"Dy": 0.06443,
"Sm": -0.02247,
"Nd": 0.03763,
"La": 0,
"Pr": 0,
"Sc": 0,
"Al": 0,
"Ca": 0,
"Fe": 0,
},
)
self.B0 = Param(
self.element_list,
initialize={
"Ce": -1.66021,
"Y": -2.12601,
"Gd": -2.24143,
"Dy": -2.42226,
"Sm": -2.12172,
"Nd": -1.62372,
"La": -1.93,
"Pr": -1.48,
"Sc": 0,
"Al": 0,
"Ca": 0,
"Fe": 0,
},
)
self.B1 = Param(
self.element_list,
initialize={
"Ce": -0.38599,
"Y": 0.26612,
"Gd": 0.03065,
"Dy": -0.02538,
"Sm": 0.17414,
"Nd": -0.38096,
"La": 0,
"Pr": 0,
"Sc": 0,
"Al": 0,
"Ca": 0,
"Fe": 0,
},
)
self.K1 = Param(
self.element_list,
initialize={
"Ce": 0,
"Y": 0,
"Gd": 0,
"Dy": 0,
"Sm": 0,
"Nd": 0,
"La": 0,
"Pr": 0,
"Sc": 632.4976,
"Al": 0.0531,
"Ca": 0.0658,
"Fe": 0.1496,
},
)
self.K_corr = Param(
self.element_list,
initialize={
"Ce": 0,
"Y": 0,
"Gd": 0,
"Dy": 0,
"Sm": 0,
"Nd": 0,
"La": 0,
"Pr": 0,
"Sc": 1,
"Al": 1,
"Ca": 1,
"Fe": 1,
},
)
@classmethod
def define_metadata(cls, obj):
obj.add_default_units(
{
"time": units.hour,
"length": units.m,
"mass": units.kg,
"amount": units.mol,
"temperature": units.K,
}
)
@property
def reaction_block_class(self):
if self._reaction_block_class is not None:
return self._reaction_block_class
else:
raise AttributeError(
"{} has not assigned a ReactionBlock class to be associated "
"with this reaction package. Please contact the developer of "
"the reaction package.".format(self.name)
)
def build_reaction_block(self, *args, **kwargs):
"""
Methods to construct a ReactionBlock associated with this
ReactionParameterBlock. This will automatically set the parameters
construction argument for the ReactionBlock.
Returns:
ReactionBlock
"""
default = kwargs.pop("default", {})
initialize = kwargs.pop("initialize", {})
if initialize == {}:
default["parameters"] = self
else:
for i in initialize.keys():
initialize[i]["parameters"] = self
return self.reaction_block_class(
*args, **kwargs, **default, initialize=initialize
)
class _SolventExtractionReactionsBlock(ProcessBlock):
default_scaler = SolventExtractionReactionScaler
