The Catalyst Review December 2019 - 13

SPECIAL FEATURE
Granulation by the "alginate" dropping process is a soft chemistry
Figure 10. Description of the "alginate" dropping shaping method
method that has been patented and developed by SINTEF, Oslo
developed and patented by SINTEF.
(Norway) for controlled MOF-sphere production (Spjelkavik et al.,
2014). Alginate/water droplets "coagulate" into a well-shaped sphere
when dropped into a water solution containing a multi-valent cation
like Ca2+ (Figure 10). The metal ion cross bind the alginate biopolymer
into a three-dimensional network with the same size as the droplet.
Such 3D spheres can be separated from the water solution and dried
leading to spheres.
The alginate dropping method is a low-cost process that can be used
for all water stable powder when well-shaped beads are needed.
SINTEF has demonstrated the production of MOF spheres with well
controlled sizes ranging from around 0.1 up to 3 mm. The shaping
Source: Blom, 2019.
demonstrator was equipped with 3D-printed multi-nozzles and a
rotating reactor to increase the productivity.
Table 3. Results of the "alginate" dropping method.
Continuous production can be carried out
with the optimized residence time in both
the cross-bonding solution and washing.
The throughput for this demonstrator lies
between 100g and 1 kg/day depending on
the sphere size. For small spheres (<0.8
mm), a spray system was used instead of
nozzles with a throughput of around 100200 g spheres per hour. Results of the study
are summarized in Table 3. In most cases
the spheres have sufficient physical strength
with crushing strength over 15-20 N. SINTEF
has produced large batches of several liters
of 0.3-0.7 mm beads of Al(OH)-fumarate and
UiO-66-fumarate showing excellent water
adsorption/desorption properties for water
Source: Spjelkavik, 2014.
harvesting applications (Meunier 2017).
In the early years of their discovery, there was a race to the discovery of structures with the largest pore size and the vision of MOF
research was mainly dominated by crystallographic aspects. Yet, catalysis is essentially a surface science where the nature of surface
termination including defects are potentially catalytic sites. We have shown here that thermal or chemical post-treatments can be
efficient and low-cost processes to generate "defective" MOFs which exhibit superior catalytic performances than state of the art
catalysts.
Conclusion
The maturity of production technologies of MOFs now ticks many boxes: raw material availability at very low price (a few USD/
kg), continuous synthesis and shaping production process at low cost which use water or non-solvent, readily available industrial
equipment's with high throughput, low environmental impact, thermal-, chemical, -mechanical stability which meet at least
minimum requirements, safety and low toxicity aspects. Over the last few years, start-ups in Europe and USA offer tens of kg
of various MOFs as powders on demand. In addition, MOF bodies of tailor-made shape and size can be produced using mature
processes like tableting and extrusion. Fortunately, MOFs which have been upscale at 10s of kg scale for demonstration purposes
have also shown potential for catalytic applications such as UiO-66, MIL-100(Fe), ZIF-8 and HKUST-1. Yet, the market of catalysts is
so competitive and mature, that the room for innovation remains extremely narrow. Nevertheless, recent years have acknowledged
major progress towards the industrialization of MOFs. Let's see what the future brings.
References
Axel'One (2019), www.axel-one.com.
Blom, R., (2019) SINTEF, www.sintef.no/en/.
Carne-Sanchez A, Imaz I, et al. (2015). "A Spray-drying Strategy for Synthesis of Nanoscale Metal-Organic Frameworks and Their Assembly
into Hollow Superstructures." Nature Chemistry, 5: 203.
Chizallet C, Lazare S, Bazer-Bachi D, et al. (2010). "Catalysis of Transesterification by a Nonfunctionalized Metal-Organic Framework:
Acido-Basicity at the External Surface of ZIF-8 Probed by FTIR and ab Initio Calculations." J. Am. Chem. Soc., 132: 12365.
The Catalyst Review 										

December 2019

13


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The Catalyst Review December 2019

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