Technology

Catalytic Ozonation with Ceramic Membrane

Uses of technologies:

Disinfection, oxidation of inorganic compounds, oxidation of organic compounds, including taste, odor,
color removal and particle removal

AOP has 2 types: combination of chemicals, catalytic reaction

Process Combination
Chemical O3/pH
O3/ H2O2
Photochemical Processes O3/ UV
H2O2/UV
Catalytical (Homogeneous) Fe2+ or Fe3+/ H2O2 or O3/UV
Heterogeneous Photocatalysis TiO2/ H2O2 or O3/UV

Can try exploring different targets, different catalyst, different phases of operation. (should we go for
gas water only, or 3 phase system)

Goal of catalytic ozonation:

- Improve oxidation efficiency to overcome the limitations in target compound removal and / or
efficient ozone use compared with AOP and conventional ozonation. (but with different target
compound)
o Activated Carbon (landfill leachate, textile wastewater)
o Al2O3 (oxalic acid), Fe2O3/Al2O3 (chloroethanol), TiO2/Al2O3 (chlorophenol)
o Fe2+, Mn2+, Cu2+ or MnO2, Ni2O3, Fe2O3 m-dinitrobenzene (m-DNB)

The target mostly on oxalic acid, chloroethanol, chlorophenol, nitrobenzoic acid.

- Achieve a higher degree of mineralization, especially with respect to the already highly oxidized
end products of oxidation processes, such as carboxylic acids. This can reduce or prevent
bacterial regrowth in the following systems, which is an important subgoal in drinking - water
applications.
o TiO2 (oxalic acid)
o CuO/Al2O3, Cu(II) (oxalic acid)
o Homogeneous Fe(III), Fe2O3 (oxalic acid)
o Activated carbon, homogeneous and heterogeneous catalyst (pyruvic acid)
o Homogeneous catalysts (citric acid)
o Granular supported metal for (30 organic compounds found in wastewater)
Subgoal: prevent bacterial growth

o TiO2 fixed on alumina beads (synthetic fulvic acid)

o Sintered iron oxide nanoparticles (biodegradable organics, bacteria)
- Achieve a more selective oxidation of target compounds, especially by oxidation in the sorbed
state.
- Reduce the influence of scavengers or promote hydroxyl radical reactions at unusual conditions,
like low pH, by oxidation in the sorbed state.

If these goals are met, catalytic ozonation can result in less ozone consumption and better economic
efficiency.

2 mechanims:

- Direct oxidation
- Indirect oxidation

Need to consider initiator, promoter, scavenger. How to produce more OH radical for indirect oxidation.

Another possible goals of ozonation:

Increase solubility of both ozone and target in the solvent

High rate selective direct reaction between ozone and compounds

Achieve higher rate of target removal.

In order to increase solubility, solvent must be:

- Low vapour pressure

- Non-toxic and immiscible with water
- High ozone solubility
- Inertness against ozone
- High affinity for the target compounds

Efficiency of different catalysts depends on:

- Chemical, crystallographic and morphological nature of catalyst

- Surface properties of the catalyst (e.g. point of zero charge (PZC), specific surface area, and
porosity
- pH and the nature of the inorganic and organic compounds present in the solution
- Chemical stability of the catalyst during the ozonation process (to avoid leaching and adsorption
without desorption)

Intrinsic physicochemical properties of currently used heterogeneous catalyst. pH will affect the
protonation and deprotonation such that the opposite charge will help in adsorption of the organic
molecule on the catalyst to facilitate oxidation, then same charge will help to separate. So be careful of
the pKa.

Need to understand the catalytic activity of the metal oxides used for heterogeneous catalytic
ozonation.

Stability towards lixiviation and catalyst inhibition by adsorption.

Need to check the process configuration

Before filtration? After filtration? Or during filtration

How to fix the catalyst, dispersed? Supported?

For research topic:

General is catalytic ozonation coupled with ceramic membrane. The general question is how to treat
pharmaceutical waste/ personal care product wastewater.

1. Understand the compounds that I want to treat PPCP (pharmaceuticals and personal care
products). (ibuprofen? Diclofenac? Or any other pharma waste, salicylic acid?). or agricultural
waste like insecticides, herbicides, OCPs. How effective is ozonation on those products? Dosage
required? pH? What catalyst is suitable? How about incorporating the process with ceramic
membrane? Should I add other oxidizing agent like H2O2? Does two stage ozonation with
different catalyst helps in enhancing degradation of compounds?
2. How about initial concentration of wastewater? Combining with other methods like UV or
sonolysis to get better removal efficiencies for pharmaceuticals

3. I think the process is governed by oxidizer concentration, rate of HO. radical formation, water
constituents, chemical structure of the pharmaceutical and solution pH. In addition to that,
other factors like concentration of H2O2, UV light intensity, or maybe intensity of ultrasound
can improve removal/degradation.

4. PS: Mechanisms are important, different combinations of methods will give different result as
there will be different reaction mechanisms of the HO. and SO4.- radicals with the
pharmaceuticals and also due to the discrepancies in their optical properties (e.g. quantum yield
and molar absorption coefficients).
5. Check degradation vs removal? How to reduce the amount of Ozone being used?
6. Another possibility is shape of the ceramic membrane, length and maybe flowrate.
7. Combining sonolysis with other AOP can achieve higher mineralization level.
8. What are the factors that cause inhibition to the effectiveness of oxidation? The inhibition rate
may be due to functional groups such as carboxyl, aliphatic hydroxyl and aryl groups present in
the organic matter.
9. What are the fates of ozonation by products? From my understanding, the permeate leftover
will be something that cannot be oxidized anymore. Something like carboxylic acid or ketone.
 10. Does adjusting the pH at different stage will help in catalytic ozonation? If certain compounds
can be protonated and some are deprotonated. Different charges can stick and improve
oxidation. Then making all of them same charge (anion) will help in separation.
11. Can we use real life mixture of wastewater?
12. Focus on quality of treated effluent (toxicity) and maybe subsequent treatment to meet
discharge limit.
13. How to maximise amount of radicals like ozone and OH.-?
14. Can we clear out inhibitors before ozonation?
15. Find optimum condition pH temperature for any particular component and catalyst.
16. Compare between catalyst for the same process
17. Learn leaching. shape of the used catalyst affect the anti-fouling effect. The long-term stability of
the coated membranes is a key issue for further development and use of catalytic ceramic
membranes. Adsorption of organic compounds at the catalyst surface can be a problem because
the whole catalyst is no more accessible and the fouling can become important. The catalyst
leaching is also a key point for the sustainability of the functionalized membranes. Literature
was not very abundant on this topic and the results are very different between the different
publications.
18. Ozonation can be performed directly in the membrane module and not in a pre-ozonation
reactor. Only papers dealing with ultrafiltration ceramic membranes coupled with catalytic
ozonation were found. As for organic membranes, fouling is reduced when ozone is applied. This
phenomenon is also observed when a catalyst is added in suspension.
19. The chemical composition and the microstructure of the catalyst influence the final anti-fouling
performances. Again depends on the operating conditions.
20. The advantage of ceramic membranes is that the catalyst can be easily coated and fixed at the
membrane surface. Among the available catalysts, iron oxides and manganese oxides have been
mainly studied giving promising results. According to some studies, iron oxide catalysts can
double the COD removal while some authors did not notice any improvement about the TOC
removal using Fe2O3.
21. On the other hand, it is crucial to be sure that the catalyst is weakly lixiviated in water and that
the adsorption of the pollutants on catalyst remains low enough.
22. Check toxicity. If the water is not toxic, can reduce cost.

Performance of catalytic ozonation with membrane depends on the nature of pollutants.

Difficult to rank catalysts because process is conducted at different condition.

So, it would be interesting to implement such ceramic nanofilters coupled with catalytic ozonation.
Nanofiltration would enable a better selectivity and retention of very small molecules (like ozonation by-
products) and a higher efficiency as contactors for catalytic ozonation.

During membrane filtration, concentrated retentates are produced.

Thanks to ozonation, retentates may have better quality and biodegradability. Some researches should
be conducted to examine more in depth this aspect. Permeates present usually a quality which is
enough to be reused. It is a strong advantage of this hybrid process.

It is important to notice that the by-products generated during ozonation are not enough studied as well
as their toxicity. Mechanistic studies are needed about identification of degradation pathway during
such coupling, fate of by-products, and toxicity of the effluent.

In the literature, the long-term stability of the membrane is not always mentioned whereas it is a key
issue for future uses in industry and in water treatment plants. The irreversible fouling and the possible
release of catalyst should be investigated in further studies about catalytic membranes.

Finally, the mechanisms of OH. production by catalyst stay not well understood and deserve to be better
clarified.