Demo case in Rosignano, Italy (CS3), operational, version 2

1. D1.2Operational demo cases
KWB, EUR, UNIVPM, KWR, GtG, AQUALIA, GSR, UCRAN, SUEZ RR,
KALUND

2. 2
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Rosignano
Lead partner (PPP site operator):
Other partners:

3. 3
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Situation before Ultimate
3.8 Mm3/y
2.0 Mm3/y
Unpredicted
Unacceptable quality
of wastewater
saltwater intrusion
FLOW
SPLITTER
To surface water body
To ARETUSA
To ARETUSA
To surface water body
Wastewater to reuse
Drinking water from industrial wells

4. 4
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
Irrigation
Match-making tool
CS3: Objectives of the Ultimate solutions

5. 5
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Subtask 1.4.2 Status/progress
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
Baseline technology: No material reuse is in place so far
Ultimate solution to foster circular economy: Adsorption pilot with alternative GAC, and AOP pilot
TRL: 4  7
Capacity: < 50 m3/h
Quantifiable targets: > 10% material recovery
Status/progress:
• detailed design completed
• construction of adsorption pilot completed
• AOP pilot under construction

6. 6
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
MATERIALS (BY-PRODUCTS) CARACTERIZATION
COMMERCIAL ACTIVATED CARBON (CA)
Laviosa Chimica Mineraria SpA extracts, process and distributes industrial mineral
products, in particular bentonitic products and special ‘modified’ bentonitic products called
“Organo-clay”. From the necessary purification stages in the organo-clay production process
comes this ‘grit’ that is poor in bentonite but rich in zeolite and other silicates.
ORGANOCLAY (LAV1)

7. 7
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
Physical activation – ATT1
• Heating of the char pellets in a tubular oven up to 700°C (5°C/min) with N2
purging.
• CO2 flushing and isotherm for 2 hr.
• Cooling of the tubular furnace in N2 purging.
Chemical activation – ATT5-ATT6/7
• Mixing of the char pellets (previously grounded) with KOH in flakes (KOH to char
ratio: 1:1).
• Heating in a tubular oven up to 600°C (5°C/min), isotherm at 600°C for 1 hr and
cooling (5°C/min) with N2 purging.
• Washing with 5M HCl and demi water (up to pH 7).
• Drying at 105°C until constant weight.
Chemical activation – ATT4
• Impregnation of char pellets in KOH aq. solution (KOH to char ratio: 1:1) at 60°C
for 6 hr.
• Drying of the impregnated char at 105°C.
• Heating in a tubular oven up to 600°C (5°C/min), isotherm at 600°C for 1 hr and
cooling (5°C/min) with N2 purging.
• Washing with 1M HCl and demi water (up to pH 7).
• Drying at 105°C until constant weight.
47%
WEIGHT
LOSS
55%
WEIGHT
LOSS
60%
WEIGHT
LOSS
MATERIALS (BY-PRODUCTS) CARACTERIZATION: HYDROCHAR ACTIVATION

8. 8
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
MATERIALS (BY-PRODUCTS) CARACTERIZATION
 RAW (NOT ACTIVATED) HYDROCHAR CONTAINS TAR  HIGH COD
 NEED OF PRE-TREATMENT (WASHING) OF RAW HYDROCHAR (NOT ACTIVATED)
 COMMERCIAL ACTIVATED CARBON (CA)
WAS USED AS REFERENCE FOR THE
ADSORPTION TESTS
 HIGH SURPHACE AREA DEVELOPED BY
ACTIVATED HYDROCHAR
LAV 1
Organo Clay
HC
Hydrochar
HC ATT 1
Activated HC
HC ATT 4
Activated HC
HC ATT 5-6-7
Activated HC
CA1
Activated carbon

9. 9
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
ADSORPTION TESTS
Material tested: Activated Hydrochar (AH) and Commercial Granular Activated Carbon (GAC)
KINETIC AND ISOTHERM FOR COD ADSORPTION IN MUNICIPAL WASTEWATER
 AH has a higher % of COD removal in a
shorter time: in the first 8 hours 60% of
COD was removed with HA and 25% with
GAC.
 Adsorption processes in both AH and GAC
can be described by Pseudo Second Order
kinetic model, while the Langmuir Isotherm
model showed a better fit than the
Freundlich model.
 100 mg and 70 mg of COD was removed by
AH and GAC respectively after 72 operating
hours.
AH AH AH
AH

10. 10
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
ADSORPTION TESTS
Material tested: Activated Hydrochar (AH) and Commercial Granular Activated Carbon (GAC)
KINETIC WITH DICLOFENAC SOLUTION
Experimental Setup for Batch Tests
 AH showed higher adsorption capacity
than conventional GAC.
 The adsorption equilibrium was reached,
after 72 operating hours for HTC and after
144 hours for GAC
0.0
50.0
100.0
150.0
200.0
250.0
0 20 40 60 80
qe
(mg
DCF
/
g
Adsorbant)
Time (h)
DCF Behaviour at 100 mg/L
AH
GAC
0.00
0.20
0.40
0.60
0.80
1.00
1.20
0 50 100 150 200
C/C0
operating hours
DCF Behaviour; GAC
A - 100 mg/L
B - 80 mg/L
C - 60 mg/L
D - 40,0 mg/L
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 20 40 60 80
C/C0
operating hours
DCF behaviour; HTC
A-100 mg/L
B-80 mg/L
C-60 mg/L
D-40 mg/L
AH
AH

11. 11
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
ADSORPTION TESTS
Material tested: Pyrolyzed Hydrochar (PH) and Commercial Granular Activated Carbon (GAC)
KINETIC WITH MUNICIPAL WASTEWATER
 PH has a slower adsorption kinetic of COD
compared with AH and GAC. Lower COD
removal was observed.
Hydrochar (HC) PH Hydrochar
SP
 Pyrolyzed hydrochar (PH) is much more
chopped and less compact.
 Thermal process effectively eliminated the
organic part (TAR) from the material.
Adsorption on Activated Hydrochar (AH) Adsorption on Pyrolyzed Hydrochar (PH)

12. 12
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Results of the functional test
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
SOFTENING/COAGULATION/FLOCCULATION TESTS
 “Precotto”: granulated limestone rocks only partially calcinated and slacked, with a declared content of Ca(OH)2
of about 9%.
 Na2CO3 “Soda Solvay® Light” product that resulted to be out of specification.
Solvay Chimica Italia
SpA by-products tested
MATERIALS (BY-PRODUCTS) CARACTERIZATION
 Solvay by-products
proved to be successful in
reducing COD and, even if
with lower
performances, Magnesiu
m and Calcium as well
 Final test are going to be
performed to optimize the
dosage
SUBSTRATE SOFT. AGENT pH COD Removal (%) Mg Removal (%)
Ca Removal
(%)
Influent municipal
wastewater
Commercial SODA 1M 8.5-10 0 < 53
Influent municipal
wastewater
Soda Solvay 8.5-10 0 44-80
Influent municipal
wastewater
Precotto 8.5-10 4-8 < 35
Influent municipal
wastewater
Precotto 8-9.5 49-58 0 17-24
Effluent wastewater Precotto 8-9.5 25-40 7-19 0
Effluent wastewater Soda Solvay 8-9.5 < 10 0 7-45
Aretusa wastewater Precotto 9-9.5 7-47 9-11.4 5.7-9
Aretusa wastewater Soda Solvay 9-9.5 47-73 0-8.4 9-24
Aretusa wastewater
Precotto and Soda
Solvay
9-9.5 80-87 4-6.2 10-24

13. 13
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Pictures/videos of the new technologies
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
ADSORPTION PILOT SYSTEM CONSTRUCTION

14. 14
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Pictures/videos of the new technologies
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
ADSORPTION PILOT SYSTEM START-UP

15. 15
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Operational procedures and methodologies
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
 Pilot plant has been designed to use
adsorption columns both in series and in
parallel
 The pilot is able to work with different flow
rates in order to optimize the operation of
bigger and smaller columns.
 Pressure in all the columns will be
monitored online to check when it is
necessary to proceed with back-washing
operations that will be carried out with a
counter-current water flow.
 Conductivity, pH and COD (UV/Vis and
fluorescence) will be monitored at the exit
of the pilot. COD will be monitored also in
the incoming flow.
 All sensors, pressure transmitters and
pumps will be connected to the electrical
cabinet and data will be available online
 The pilot will be firstly installed and
operated at the pilot hall of UNIVPM and
than will be transported and installed at
ARETUSA site
ADSORPTION PILOT SYSTEM

16. 16
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Operational procedures and methodologies
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
SKID EQUIPPED WITH:
 pressurization pump: 60 l/min, 1.9 bar
 sand filter: 3.5 mc/h 250 kg of sand
 multi-cartridge filter
 electromagnetic dosing pump
 static mixer
 Viqua PRO 24-180mJ UV system
 electrical panel
AOP PILOT SYSTEM
Pilot plant under construction!

17. 17
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: First results
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
INFLUENT EFFLUENT
Fluorescence (I5): 0.932
UV: 0.1246
Fluorescence (I5): 0.559
UV: 0.077
Fluorescence (I5): 0.408
UV: 0.043
Fluorescence (I5): 0.110
UV: 0.0104
Calibration of the fluorescence sensor showed
promising results!
ADSORPTION PILOT SYSTEM

18. 18
The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3: Subtask 1.4.2 – Timeline
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
M1
M2
M3
M4
M5
M6
M7
M8
M9
M10
M11
M12
YEAR 1 YEAR 2 YEAR 3 YEAR 4
 Pilot system is operational since July 2022 (M26)
 Still enough time to complete the pilot experiments
Legend
Task/Subtask
Activity as planned
Postponed activity
Delay of activity
Subtask: 1.4.2 Use of by-products of local industries for wastewater treatment in Rosignano
T1.4.2 - Use of by-products of local industries for wastewater
treatment in Rosignano
Baseline conditions assessed MS05 D1.1
Design of pilot system MS09
Laboratory scale experiments MS15
Pilot system operational MS15 + 8M D1.2 + 2M
Start-up & results MS19 D1.9
Best practices for material recovery D1.5

19. The project leading to this application has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 869318
CS3 Contacts
c.bruni@pm.univpm.it
f.fatone@univpm.it
mattiaciampechini@gmail.com
m.sgroi@univpm.it