Post on 29-Nov-2021
Giuseppe Mancini – gmancini@dii.unict.it 1 IWWATV Conference Athens 2015
Small improvements in the treatment of oily wastes from marine
transportation
University of CataniaDepartment of Industrial
Engineering
G. Mancini, M. Panzica, E. Palmeri, S. Cappello, M. M. Yakimov, A. Lucianogmancini@dii.unict.it
IWWATV Athens May 21-23 2015
Giuseppe Mancini – gmancini@dii.unict.it 2 IWWATV Conference Athens 2015
…….
The role of marine transport
Giuseppe Mancini – gmancini@dii.unict.it 3 IWWATV Conference Athens 2015
…….
European Transport Policy
shipping and related maritime industries are important contributors to the European GDP
European Transport Policy“underlined the importance of developing maritime transport and favor interconnection. “a need for new ideas in transport logistics planning, involving not only ports and shipping operators, but the entire chain that brings goods from the factory to the final consumer. Ship services need to operate regularly to develop this concept, in order to create an alternative to road transport”.
“the necessity to assure the sea connection”; The concept of Motorways of the Sea”. “the need for favorable technical conditions, such as quality of port services, quality of hinterland connections, information systems and monitoring in transport logistics, and special characteristics of ship services (frequency and regularity, safety and security);
--- CO2- emissions shipping<<< any other transport mode
Giuseppe Mancini – gmancini@dii.unict.it 5 IWWATV Conference Athens 2015
…….
Marine Transport in the Mediterranean Sea
Giuseppe Mancini – gmancini@dii.unict.it 7 IWWATV Conference Athens 2015
Oily wastewater and oil-water emulsion are two of the mainpollutants discharged to water environment, through ordinaryoperations These waste(water)s are generated by ships mainly inengine-rooms (bilge waters) and by washing oil tanks (slops) inamounts of millions of tons annually.
Background
Giuseppe Mancini – gmancini@dii.unict.it 8 IWWATV Conference Athens 2015
These issues are particularly critical in Mediterranean Sea that hasbeen defined as a “Special Area” by the international Law MARPOL73/78 (IMO, 1973/1978) that strictly forbids any mineral oil or oilymixtures to be directly discharged to the sea by oil tankers. Directive2000/59/EC and 2005/35/EC put much further pressure on thecollection by harbour authority.
Background
Giuseppe Mancini – gmancini@dii.unict.it 10 IWWATV Conference Athens 2015
BackgroundSlops are wash-waters originated from the cleaning of oil tankers.Beside the presence of refractory compounds, these waters show extremely highsalinity levels (up to 25.000 p.p.m.), that limit the possibility of discharge to sewersand address the disposal to the sea.
This severely lowers the concentrations limits for most of the “sensible”parameters, such both COD and xenobiotic hydrocarbons, thus requiring a higherlevel treatment.
Giuseppe Mancini – gmancini@dii.unict.it 11 IWWATV Conference Athens 2015
Introduction
Many of these fluids are verystable emulsion, which makeconventional treatment difficult.
The water phase from chemical treatment has to befurther treated. This is often achieved by granularactivated carbon (GAC) filtration (Ha et al., 2000).
The most diffused method fortreatment of emulsified oilywastewater is de-emulsification followed byclarification, which requiresthe use of a variety ofchemicals such as sulphuricacid, iron and aluminasulphates, ect. Shut'ko (1986)
Giuseppe Mancini – gmancini@dii.unict.it 12 IWWATV Conference Athens 2015
IntroductionHowever GAC regeneration costs so interest has risen on bioregeneration ofexhaust GAC.. Little work has been done on the biodegradation and adsorptionof salty mixtures of biodegradable and non-biodegradable SOCs
The normal bacteria which are growing in CAS or MBR cannot withstand at theseadverse conditions, therefore it is necessary to be adapted (Lefebvre and Moletta,2006).
A few studies (Reid et al., 2006; Artiga et al., 2008; Llop et al., 2009; Soltani et al.,2010) have dealt with this issue (adapting the microorganism) but still a lack ofinformation is observed for applying biological treatment for high salinity oilywaters.
Giuseppe Mancini – gmancini@dii.unict.it 13 IWWATV Conference Athens 2015
Research Project
3) Project PON02_00153_2849085 (Projecttitle: STI-TAM Development ofInnovative technologies for the treatmentof fluid wastes from shipping activitiesand for marine environment protection,PON&REC 2007/2013)
2) The Italian Ministry of Education, University and Research (MIUR), throughthe program “Research Program of Relevant National Interest”, PRIN2010ARBLT7 (Project title: Systems biology in the study of xenobiotic effectson marine organisms for evaluation of the environmental health status:biotechnological applications for potential recovery strategies)
1) Project PON02_00153_2939551 (Project title: Development of innovativetechnologies for energy saving and environmental sustainability ofshipyards and harbour areas – SEAPORT, PON&REC 2007/2013)
Identification of liquid wastetypes and sampling
WP
1: S
ampl
ing
and
char
acte
riza
tion
of
liqui
d w
aste
s fro
m
ship
ping
act
iviti
es
= Check of process efficiency and observance of the limits to the dischargeV
In situ de-oiling
Wastewaterscharacterization
WP 2: C
hemical
treatment by
means
oftotal catalyticoxidation
Testing of total catalyticoxidation
Testing of physical/chemical pre-treatment into batch reactors
Adsorption tests on phyllosilicates Adsorption runs on
modified AC
Adsorption on AC and BAC
WP
3:
Phys
ical
/che
mic
al
trea
tmen
t of d
e-oi
led
wat
ewat
ers
Photo-catalytic tests Experimental runs of MBR biological tratment
WP
4: T
reat
men
tsby
mea
nsof
cata
lytic
tech
niqu
es
Experimental runs of BF-MBR biological tratment
Electro -catalytic tests
Testing of biologicalA.C. bio-regeneration
WP 5: M
embrane
biologicaltreatm
ent
Target: Discarge to the sea
WP6
: Pro
toty
pe p
hase
: ac
hiev
emen
ts in
fixe
d,
mob
ile, o
r tr
ansp
orta
ble
pilo
t sca
le tr
eatm
ent
plan
t
Design
Construction of pilot plants
Design and navalization
Experimental demonstrator
VV V
V
V
Catalytic denitrificationtests
Giuseppe Mancini – gmancini@dii.unict.it 15 IWWATV Conference Athens 2015
Pilot Plant (Cantieri navali di Augusta)
Chemical Engineering for industrial sustainability
Giuseppe Mancini – gmancini@dii.unict.it 16 IWWATV Conference Athens 2015
Wastewater sampling and on site pre-treatment
Giuseppe Mancini – gmancini@dii.unict.it 17 IWWATV Conference Athens 2015
Wastewater sampling and in situ pre-treatment
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Wastewater sampling and in situ pre-treatment
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Wastewater sampling (Dockyard)
Giuseppe Mancini – gmancini@dii.unict.it 20 IWWATV Conference Athens 2015
Experimental ActivitiesDiesel Slops Pre‐Treatment‐ De‐Oiling‐ Coagulation
Ferric chloride (FeCl3)Aluminum sulfate (Al2(SO4)3) Polyaluminum chloride (Al2(OH3)Cl3)Organic flocculant
Giuseppe Mancini – gmancini@dii.unict.it 21 IWWATV Conference Athens 2015
Jar test on slops: TPH removal
50
3 3
0
10
20
30
40
50
60
R aw water 50 70
F erric chloride (mg/l)
TPH (mg/l)
R aw waterF erric chlorideF erric chloride + 5 mg/l polyelectrolyteDis charge limit to the s ea
<d.l. <d.l.
99%
Giuseppe Mancini – gmancini@dii.unict.it 22 IWWATV Conference Athens 2015
Jar test on slops: COD removal
1310
1670
1170963 1055
633
11501260
718880
584
0
500
1000
1500
2000
2500
30 40 50 60 70 100 150 200
Ferric chloride (mg/l)
Res
idual C
OD (mg/l)
Ferric chlorideFerric chloride plus 5 mg/l polyelectrolyteTrend of res idual COD us ing ferric chloride plus 5 mg/l polyelectrolyte
47%
Giuseppe Mancini – gmancini@dii.unict.it 23 IWWATV Conference Athens 2015
RESULTSSlops and Dockyard characterization
Parameters Units ex diesel slops
dockyard waters
pH 7.0 7.4 Light hydrocarbons from C6 to C10 (mg/l) < 0.01 0.80 Heavy hydrocarbons from C > 10 to C20 (mg/l) 6.66 143.99 Heavy hydrocarbons from C > 20 to C30 (mg/l) 2.72 72.00 Heavy hydrocarbons from C > 30 to C40 (mg/l) 0.49 74.57 Heavy hydrocarbons from C > 40 to C50 (mg/l) < 0.006 3.52 Sum of heavy hydrocarbons from C > 10 to C50 (mg/l) 9.88 294.09 TPH from C6 to C50 (mg/l) 9.88 294.89 TOC (mg/l) 114.8 478.5 COD (mg/l) 301.0 930.0 Chlorides Cl- (mg/l) 20320.0 809.0
Giuseppe Mancini – gmancini@dii.unict.it 24 IWWATV Conference Athens 2015
Jar test on slops: COD removal
0
10
20
30
40
50
60
70
80
90
100
50 60 70 80 90 100 50 60 70 80 90 100 10 20 30 40 50 60
CO
D re
mov
al [%
]
Coagulant dosages [mg/l]
Ferric chloride pH 7 Aluminum sulfate pH 7 Polyaluminum chloride pH 7
Giuseppe Mancini – gmancini@dii.unict.it 25 IWWATV Conference Athens 2015
Jar test on slops: COD removal
0
50
100
150
200
250
300
350
400
50 60 70 80 90 100 50 60 70 80 90 100 10 20 30 40 50 60
CO
D [m
g/l]
Coagulant dosages [mg/l]
Ferric chloride pH 7 Aluminum sulfate pH 7Polyaluminum chloride pH 7 Initial value
Giuseppe Mancini – gmancini@dii.unict.it 26 IWWATV Conference Athens 2015
Jar test on slops: sludge production
0102030405060708090
100110120
10 20 30 40 50 60 70 80 90 100
Set
tled
slud
ge [m
l/l]
Coagulant dosages [mg/l]
Ferric chloride pH 7 Aluminum sulfate pH 7 Polyaluminum chloride pH 7
Giuseppe Mancini – gmancini@dii.unict.it 27 IWWATV Conference Athens 2015
Jar test on dockyard waters: COD remov.
0
10
20
30
40
50
60
70
80
90
100
CO
D re
mov
al [%
]
Coagulant dosages [mg/l]
Ferric chloride pH 7.4 Aluminum sulfate pH 7.4 Organic flocculant pH 7.4
Giuseppe Mancini – gmancini@dii.unict.it 28 IWWATV Conference Athens 2015
Jar test on dockyard waters: COD remov.
0
100
200
300
400
500
600
CO
D [m
g/l]
Coagulant dosages [mg/l]
Ferric chloride pH 7.4 Aluminum sulfate pH 7.4Organic flocculant pH 7.4 Initial valueDischarge limit (D.Lgs. 152/06)
Giuseppe Mancini – gmancini@dii.unict.it 29 IWWATV Conference Athens 2015
Jar test on dockyard waters: sludge prod.
05
10152025303540455055
20 30 40 50 60 70 80 90 100 300 3000
Set
tled
slud
ge [m
l/l]
Coagulant dosages [mg/l]
Ferric chloride pH 7.4 Aluminum sulfate pH 7.4 Organic flocculant pH 7.4
Experimental ActivitiesDiesel Slops Adsorption & Kinetic StudiesCo
agulant: FeCl
370
mg/L
GAC
: Filtrasorb 400
Parameter: TPH
Experimental ActivitiesDiesel Slops Adsorption & Kinetic StudiesCo
agulant: FeCl
370
mg/L
GAC
: Filtrasorb 400
Parameter: TOC
Experimental ActivitiesDiesel Slops Adsorption & Kinetic StudiesCo
agulant: FeCl
370
mg/L
GAC
: Filtrasorb 400
Parameter: C
OD
Giuseppe Mancini – gmancini@dii.unict.it 33 IWWATV Conference Athens 2015
Experimental Activitiesavio Jet A‐1 Slops Adsorption & Kinetic Studies
Coagulant: Al
2(SO
4)370
mg/L
GAC
: Filtrasorb 400
Parameter: C
OD
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First respirometric tests results
Respirometric batch test of CAS bacteria fed with slop
Respirogram of acclimatized biomass from a CAS process with the addition of sodium acetate
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Main goal of the research activities(GAC on-line Bioregeneration)
MBR?
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Hybrid Moving Bed Biofilm Reactor (HMBBR) - University of Palermo)
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Halophilic bacteria from oil spills marine oil-polluted sites (CNR-IAMC)
Alcanivorax borkumensis(1998 Borkum Island, Germany)
Thalassolituus oleivorans(2004 –Milazzo Harbour, Italy)
Oleiphilus messinensis(2002 – Messina Harbour, Italy)
Oleispira antartica(2003 – Ross Sea, Antartica)
Antarctic continent
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A strain of Alcanivorax borkumensis strain SK2T (Genebank accession numberY12579; =DSM 11573T) was used in the experiments. This bacterium grows at28°C, in aerobic conditions and it is able to grow on many saturated petroleumfraction constituents
Halophilic bacteria from marine oil-polluted sites (CNR-IAMC)
Giuseppe Mancini – gmancini@dii.unict.it 39 IWWATV Conference Athens 2015
Bacterial densities determined by DAPI staining and measure of cultivable bacteria (CFU)
Photography in fluorescence microscopy (DAPI staining) of A. borkumensis SK2 during the growth in crude oil
Giuseppe Mancini – gmancini@dii.unict.it 40 IWWATV Conference Athens 2015
GAC bioregeneration (Slops):comparison of the virgin and bio-regenerated GACs
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GAC bioregeneration (dockyard wastewaters):comparison of the virgin and bio-regenerated GACs
Giuseppe Mancini – gmancini@dii.unict.it 42 IWWATV Conference Athens 2015
Qualitative improvement of the dockyard waste(water)s over the full process
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Conclusions
Pre-treatment of wastewater must be optimized for the specific treatedwaste(water)s. Generally Aluminum sulfate (Al2(SO4)3) perform betteron slops while interesting results were also obtained for the dockyardwaters through the use of the organic flocculant
Tests on bioregeneration of exhaust GAC, gave encouraging results inrecovery a relevant part of exhausted carbon absorption capacity.
Although biological treatment is usually inhibited by high saltconcentrations, results from the present research proved the feasibility ofusing salt-adapted micro-organisms consortia capable of degrading themain pollutants contained in these oily and salty contaminated waters.
Bioregeneration of GAC loaded by TPH from slops of dockyardwaste(water)s can thus increases the service-life of the GAC and, notrequiring the GAC to be removed from the filter, it can allow a furtherreduction in GAC management costs