RESOURCE RECOVERY POTENTIAL OF

MSWI FLY ASH ACID EXTRACTION

E. Korotenko 1, M. Šyc 1, J. Jadrný 2, P. Mašín 3, P. Krystyník 1, P. Klusoň 1

1 Department of Environmental Engineering, Institute of Chemical Process Fundamentals of the CAS, v.v.i.
Rozvojová 2/135, CZ-165 02 Prague 6 - Suchdol, Czech Republic
2 TERMIZO a.s., Dr. M. Horákové 571/56, 460 07 Liberec, Czech Republic

3 Dekonta a.s., Dřetovice 109, 273 42 Stehelčeves, Czech Republic

ABSTRACT: Changing legislation in the field of waste management is shifting waste management
strategies towards waste-to-energy, recovery, and recycling. Historically, municipal solid waste
incinerators (MSWI) was seen only as a way of waste disposal, but today's reality is that MSWI can
also participate in recycling. The aim of the paper was to determine the recovery potential of the fly ash
acid extraction on the real scale from data obtained from MSWI plant in the Czech Republic. The
results show, that no long-term variability of Zn content in fly ash was observed, but it varies on a short-
term/daily basis. The Zn extraction efficiency is ca 48 %. Current Zn potential for recovery is ca 50
tonnes per year, but it can be increased by 10-23 tonnes after acid extraction step optimization.

Keywords: MSWI fly ash, zinc, recovery potential, acid extraction

1. INTRODUCTION

Fly ashes (FA) and air pollution control residues (APCr) are the main solid residues from municipal
solid waste incineration process, together with bottom ash. FA/APCr production in Europe is estimated
to be ca 2 mil. tons. FA and APCr composition and characteristic are mainly given by the type of air
pollution control device, particularly for acid gases and POPs removal. APCr usually comes from dry or
semi-dry methods as resulting solid residue consists of a mixture of spent sorbent including activated
carbon with captured POPs and fly ash itself; whereas the product from air pollution control devices
(APCD) in selected types of wet methods is solely fly ash. FA/APCr are considered hazardous waste
and their hazardous properties come from high content of soluble salts, heavy metals and/or POPs. The
environmental policy of EU is currently focusing on diminishing of hazardous materials production or
methods for removal of their hazardous properties instead of landfilling.
An up-to-date overview of treatment methods with respect to circular economy and recovery
potential was prepared by Quina et al. (2018). It is obvious that due to the recent development, APCr
and FA can be also considered a secondary raw material for recovery of valuable components,
particularly for metals or salts recovery. Technologies for the recovery of metals (particularly Zn) and/or
salts are based mainly on hydrometallurgical principal and can use acid water from wet scrubber of
APCD with advantage. Several technologies are under development or on a lab scale level. However,
FLUWA/FLUREC technology works on a full-scale and HALOSEP full-scale plant is under construction.
Details about these technologies are published elsewhere (Quina et al.,2018; Weibel et al., 2018;

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Rasmussen, 2018).
The Termizo waste-to-energy plant in Liberec is equipped with FLUWA acid leaching technology for
fly ashes. Up to now, it is used only for the removal of heavy metals from FA, i.e. for the removal of their
hazardous properties. However, recent efforts have been focused also on reviewing the possibility to
recover Zn and salts within this technology. Therefore, a detailed analysis of the mass flow of selected
species has been performed for the determination of the recovery potential and economic feasibility of
the process. The results of Zn mass flow analysis within the process and process streams variability are
presented in this paper.

2. MATERIALS AND METHODS

2.1 Analyzed samples

The FLUWA process can be divided into three stages: extraction, alkalization, and treatment of
extract. Samples from all of these stages were taken. The aim of the sampling campaigns was to
describe the FLUWA process parameters of the real MSWI plant and to identify the process streams
that can be suitable for resource recovery.
For this purpose, 3 sampling campaigns were performed. Samples of the following streams were
taken: Q – technological water from the quench, which is used as an extracting agent, FA – fly ash, E –
extract from the fly ash (in the output of extraction stage), XFA – treated fly ash, O – water from the 2nd
stage of wet scrubber, XE – treated alkalized extract, WW – water to wastewater treatment plant, FC –
filter cake.
All samples, liquid and solid, were prepared by mixing of several primary samples taken with a
specific sampling frequency during one day to form an integral representative sample.

Figure 1. Samples of fly ash (FA), treated fly ash (XFA), and filter cake (FC).

2.2 Analyzed properties

The properties of liquid and solid streams were analyzed. In solid samples, always 3 replicates were

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measured. The results were statistically processed.
The contents of elements in solid materials were determined by ICP-OES in samples from
microwave digestion. For the microwave digestion, a mixture of HCl and HNO3 was used. The contents
of elements in liquid samples were also determined by ICP-OES.
Content of chlorides, sulfates, and fluorides in liquid samples was determined according to US EPA
325.1, ČSN ISO10359-1, ČSN ISO10359-2 and US EPA 375.4 respectively.
Extraction efficiency was calculated as a ratio of the output content of the element in the extract to
the input content of the element in fly ash.

3. RESULTS AND DISCUSSION

The paper summarizes the mass balance of the acid leaching process, the variability of key solid and
liquid streams, and Zn material flow analysis within the process. This data is crucial for the estimation of
recovery potential and further improvement of the process.

3.1 Composition and variability of streams

Figure 2. Variability of zinc concentration in solid streams.

The results from three sampling campaigns are presented in Figure 2; the determination of Zn content
and long- and short-term variability in fly ash (FA), treated fly ash (XFA), and filter cake (FC) was the
main objective of these campaigns. It can be concluded that Zn content in fly ash is relatively variable
on a short-term/daily basis and is within the range 29.5-47.5 g/kg. Long-term variability, i.e. increase or
decrease with respect to seasonal changes were not found. Moreover, it can be concluded there is no
obvious correlation between Zn content in raw and extracted fly ash. This means a variable efficiency of
the extraction process that is affected by several parameters like HCl concentration in the quench
water, fly ash composition, Zn chemical speciation, redox potential, etc. It is obvious also from Figure 3
as Zn concentration in the liquid extract from fly ash varies from 500 to 1700 mg/l. The content of Zn in
filter cake varies within 50-115 g/kg, that is ca two times lower than reported from FLUWA by Quina et
al. and 4-8 times lower than is necessary for filter cake utilization in the smelting industry. This means
that an overall process optimization would be necessary for Zn recovery.

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Figure 3. Variability of zinc concentration in liquid streams.

3.2 Zinc mass balance

Zinc mass balance of the process is shown in Figure 4. Zn input into the process is ca 13 kg/h, that
means a total annual Zn input of 105 tonnes. No Zn input in liquid streams can be stressed as Zn
concentration in the process water is in average 1.5 mg/l. The remaining extracted fly ash represents ca
5.24 kg of Zn per hour leading to an annual Zn output of ca 42 tonnes. The flow of Zn in the liquid
extract is ca 6.19 kg/h of Zn, this amount ended in filter cake, which means an annual Zn output of ca
50 tonnes. These 50 tonnes can be considered potentially recoverable within current technology
scheme. The overall mass balance reliability is 88 %, which is in our opinion very good, as there is high
variability of streams composition and mass balance is based on technological measurements of mass
flows of all streams.
Based on the above-mentioned data the efficiency of Zn extraction (ratio of Zn input to Zn output in
extract) is ca 48 %, which is relatively low compared to literature data (Quina et al., 2018) as they
mentioned in optimized real scale plant extraction efficiency of ca 65-80 %. This means an additional
potential for Zn extraction and then for recovery of about 10-23 tonnes of Zn per year. Nowadays, a
filter cake with low Zn content is considered hazardous waste and is landfilled, which means the loss of
Zn potential and additional costs for the MSWI plant operator. Therefore, an overall process
optimization including extraction step and alkalization is necessary for achieving of a product rich in Zn
that can be used in the smelting process. Extraction of FA is a key operation, which influences the total
yield of recoverable Zn. Zn and other recoverable metals solubility in acid water can be increased by
optimization of extraction process parameters (liquid-to-solid ratio, redox potential, residence time,
temperature and so on) and application of additives. Moreover, the change of alkalization agent from
Ca(OH)2 that forms insoluble CaSO4 (that ends in filter cake) to NaOH is another optimization step that
will be considered. All these steps will be also reviewed with respect to economic feasibility of the
process.

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Figure 4. Material flow analysis of zinc in kg per hour. Average annual production of FA, XFA, and FC (in dry
matter) is 3000 tonnes, 2300 tonnes and 235 tonnes respectively.

4. CONCLUSIONS

The aim of the paper is to determine the recovery potential of the fly ash acid leaching based on the
real scale data from an MSWI plant in the Czech Republic. For this purpose, the composition and
properties of solid and liquid streams, including their short- and long-term variability, were examined.
No long-term variability of Zn content in fly ash was observed, but it varies on a short-term/daily basis.
Moreover, the Zn extraction variability is affected by many parameters and is also very variable with an
average efficiency of ca 48 %. Current Zn potential for recovery is ca 50 tonnes per year, but it can be
increased by 10-23 tonnes after acid extraction step optimization. Zn content in the produced filter cake
is 5-11 % which is 4-8 times lower than the content required for filter cake processing in the smelting
industry. Therefore, several optimization steps are considered and will be tested, of course, also with
respect to Zn recovery economic feasibility.

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ACKNOWLEDGMENTS

This work was conducted with the support from the Technology Agency of the Czech Republic
TH04030103 and the Internal Grant Agency of the Institute of Chemical Process Fundamentals of the
Czech Academy of Sciences.

REFERENCES

Quina, M. J. et al. 2018. Technologies for the management of MSW incineration ashes from gas cleaning: New
perspectives on recovery of secondary raw materials and circular economy. Sci. Total Environ. 635, 526–542.
Weibel, G. et al. 2018. Extraction of heavy metals from MSWI fly ash using hydrochloric acid and sodium chloride
solution. Waste Mang. 76, 457–471.
Rasmussen, E. 2018. Halosep Fly Ash Treatment at Waste to Energy Plants. Retrieved from
https://www.energiforetagen.se/globalassets/energiforetagen/det-erbjuder-vi/sakomraden/askdagen/erik-
rasmussen-stena.pdf?v=WBA8SskdHU2Z-CopQZy9hNnIc1E

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