Universidad de las Américas Puebla

Selected Topics 3: Chemical Industry and Nanotechnology

November 2022

Individual Final Project

Isaac Azcárate – ID: 165970

 “MOF membrane for propane/propylene separation in the
petrochemical industry”

The constant search for efficiency in the mass production of thousands of products and services has
led hundreds of industries to optimize their processes. Whether from the study of logistics, the
particularization of the market or obtaining alternative sources of raw materials, the primary objective
is to do more with less. Added to this equation is the need to seek production methodologies that do
not leave a permanent or considerable footprint on the environment, derived from the recent doctrine
that inculcates the care of nature, and therefore the interests of health and conservation of an adequate
lifestyle for the present and future population, being the energy sector one of the main factors of this
mentality.

There are two ways to attack the problem related to energy consumption: either we seek to consume
less energy, or we devote efforts to the development of an alternative source, capable of supplying
reliably and constantly the energy already used. The best way to achieve a visible effect in the short
and medium term seems to be to reduce energy needs. It is on this point that the proposal of the
present work will focus, the separation of propane from propylene in the petrochemical industry in a
more efficient way with an advanced nanotechnological material, a Metal-Organic Framework
(MOF).

Before continuing with the description of the proposal, it is prudent to define the key piece of the
proposal: MOFs. By its acronym, Metal-Organic Framework, a MOF is a nanostructured material
characterized by its crystalline arrangement, high porosity and three-dimensional (3D) network of
interconnected metal ions from the interaction of these ions with multidentate organic ligands 1,2.
Among the multiple applications of this type of material 3,4, the separation of composites will be the
most important for our objective.

The potential of this material is of great importance for industry where compound separation is
paramount. The petrochemical industry falls into this category of industries, especially because of the
importance of the degree of resistance of the substances with which it works. The method by which
these separations are usually carried out in this field is called refining. The compounds of interest for
the project are propane and propylene, which are used as precursors to produce other chemical
derivatives 5.
The complexity of the process lies in the reduced working area in which propane and propylene gases
are separable, being the boiling points of both - 42 ºC and - 47 ºC respectively, in addition to the
almost ideal behavior of the mixture of these gases 6. Maintaining stable conditions of pressure and
temperature to establish a suitable environment that favors the separation of both compounds is
undoubtedly a challenge.

Equilibrium curve propane/propylene 6

In a common way, a distillation system has several unitary operations, in which stands out the
presence of gas compressors that make the gaseous mixture pass through a heat exchanger that
preheats the mixture before entering the distillation column, which, to avoid having a height beyond
the manageable and practical parameters, is usually divided into two sections, which are responsible
for purifying the mixture and separating the components. These are equipped with a reflux system
that promotes the purification of the compounds based on the change of mole fractions of the mixture.
Towards the outlet of the columns there are condensers that allow the recovery of propane and
propylene.

One of the alternatives is to use selective adsorption of olefin on a chemically modified nanoporous
adsorbent, since a suitable pore size can selectively separate gases with nearly identical physical
properties.7 This is the proposal of the project: to implement a MOF membrane to a refinery system
to efficiently separate propane and propylene, which would reduce the energy invested in this process
by cryogenic distillation, which is an energetically demanding process.8 The MOFs have been shown
to achieve high purity of propylene in a single adsorption-desorption process from an equimolar
mixture of propylene and propylene in an equimolar mixture of propylene.
From the investigation of MOFs as separation agents, it has been shown that they realize high purity
of propylene in a single adsorption-desorption process from an equimolar mixture of propylene and
propane, which enables good separation capability and fast adsorption-desorption kinetics 9.

Diagram of the distillation process commonly used to obtain propylene and propane.

The multilayer MOF used for membrane formation would be Ni-MOF ([Ni3(OH)2(1,4-
benzenedicarboxylate)2(H2O)4] ⋅2H2O). The synthesis proposed by Li et al 10 would be followed.
This is a solvothermal synthesis process, in which it is possible to determine the thickness of the
membrane from the ratio of reactants. These have a crystalline structure of multilayered nanosheets
whose dimensions did not exceed 60 nm. The average pore size was 2 nm. By obtaining the
adsorption-desorption isotherm for N2 gas, the specific surface area was calculated to be 15.21 m2/g,
making it a large adsorbent with many active sites.

Three proposals for the implementation of MOF in the industrial process are considered. The first
involved the use of a MOF membrane filtration unit, like that placed in home water systems for
filtration of salts and other contaminants from water. The second alternative was the functionalization
of the walls of a piping system through which the mixture would pass. Both options would be located
outside the distillation unit, i.e., they would require special infrastructure to be included in the
established process.

However, in the end it was decided to implement a MOF membrane inside the distillation column. Its
format would be like that of one of the existing distillation dishes and it would be located at the
bottom of the column. This option was selected over the previous ones because, among its qualities,
it saves the need to introduce an additional unit operation to the distillation column and performs the
separation in a more direct way. In addition, it is more efficient than doping a large surface area as
proposed with the shell heater model.

MOF membranes will be able to selectively chemisorb propylene from the mixture of both gases on
their surface which would reduce the need for a reflux of compounds in a distillation column, as is
usually done today. This would facilitate the separation of propane and offers a great degree of
strength.

Unfortunately, any proposed improvement comes with certain difficulties or aspects that define its
applicability. The first hurdle to overcome will be to gain the confidence of the industrial sector in
the use of new technologies, particularly nanotechnology, to improve already established processes.
In other words, it is necessary to convince to give a chance to the new over the proven.

Subsequently, it is to give security on the investment being made, being able to ensure the reuse of
the product in the process, which translates into savings for the customer and not a constant source of
expenses. This aspect is strongly influenced by the control of the conditions under which the product
is used. The absorption properties are primarily determined by the temperature and pressure
conditions. Adequate control of these factors implies the need for systems capable of measuring and
modifying them, if necessary, which translates into an initial investment in such technology, together
with the production of the material per se.

In addition to these, there is the need to be in accordance with the different regulatory norms of the
place where the system will be implemented. These may include regulations regarding environmental
care, modes of production, worker safety, etc.

Despite the possible constraints, we are sure of the proposal's usefulness and that after its adequate
study and application, it can generate medium and long term economic, environmental, and energetic
benefits.
References

1. Propano: fórmula y tipos de suministro. precio gas.com, 2013.

http://investiguemoselpetroleo.blogspot.com/p/productos-derivados-del-propileno-los.html
(accessed 2022-09-19).

2. Investiguemos el petróleo. Blogspot.com.

http://investiguemoselpetroleo.blogspot.com/p/productos-derivados-del-propileno-los.html
(accessed 2022-09-19).

3. C. Janiak, 2003, Engineering coordination polymers towards applications, Dalton Trans., 14,
2781.

4. B. Gomez-Lor et al, 2005, Novel 2D and 3D indium metal organic frameworks: Topology and
catalytic properties, Chem. Mater.,17, 10, 2568.

5. Investiguemos el petróleo. Blogspot.com.

http://investiguemoselpetroleo.blogspot.com/p/productos-derivados-del-propileno-los.html
(accessed 2022-09-19).

6. Wee Chong K., Surya E., Shamsuzzaman F. (2018) Industrial Scale Propylene/Propane
Separation Using Pressure Vacuum Swing Adsorption. Industrial & Engineering Chemistry
Research 57 (18), 6451-6463. DOI: 10.1021/acs.iecr.8b00289

7. B. Van de Voorde, B. Bueken, J. Denayer, D. De Vos, Chem. Soc. Rev. 2014, 43, 5766.

8. Refinación. Gob.mx.
https://www.gob.mx/cms/uploads/attachment/file/6977/Refinacion_Web.pdf (accessed 2022-
09-19).

9. Zeng, H., Xie, M., Wang, T. et al. Orthogonal-array dynamic molecular sieving of
propylene/propane mixtures. Nature 595, 542–548 (2021). https://doi.org/10.1038/s41586-021-
03627-8

10. Li, G., Qi, Y., Lin, H., Lu, N., Chen, J., Wang, J., Han, Q. & Liu, F. (2021, octubre). Ni-metal-
organic-framework (Ni-MOF) membranes from multiply stacked nanosheets (MSNs) for
efficient molecular sieve separation in aqueous and organic solvent. Journal of Membrane
Science, 635, 119470. https://doi.org/10.1016/j.memsci.2021.119470