Advanced Oxidation Technologies - Case studies in non

biodegradable wastewater treatment 

Elena Gil Aunon

Water Special Interest Group
P11
 Outline

 What AOP is?

 Summary of AOP
 Application, advantages and disadvantages
 OHP® Technology
 Case Studies

Jacobo Villagran: jacobo.villagran@peroxychem.com

Arantxa Aparicio: aaparicio@comsa.com

Marta Trillas :mtrillas@comsa.com
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 What Advanced Oxidation Process (AOP) is?
• AOP are oxidative water treatment used to treat toxic effluents.
• AOP are successful in transforming toxic organic compounds into
biodegradable substances.
• AOP are generally affordable to install but with high operating costs (due to
chemicals and energy)
• To limit costs, AOP can be installed as pre-treatment Oxidant Potential
(V)

• Recently AOP are used to remove micro-pollutants in the Fluor

Hydroxyl
3.06
2.80

• STW and as disinfection of clean/potable water. Oxone 2.07

Parmanganate 1.77
ion
• AOP involve 2 stages of oxidization: H2O2 1.67

• 1st stage: Formation of strong oxidants (hydroxyl radicals ·OH ) ClO2 1.50
Cl2 1.36
• 2nd Stage: Reaction of these oxidants with organic contaminants
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 1st stage: How ·OH is formed?
AOP Oxidant agent/Catalyst Reaction
Fenton H2O2/Fe 2+ H2O2+Fe2+ Fe3+ +OH-+·OH
Sonolysis / Cavitation Ultrasound O3+H2OO2+2·OH
Photolysis H2O2/UV H2O2·OH

Photocatalysis (Photo Fenton) H2O2/Fe 2+ H2O2+Fe2+ Fe3+ +OH-+·OH

H2O2/O3 H2O2/O3 H2O2+H2O HO2-+·OH+H3O+

O3+HO2-·OH+O2-+O2
O3/UV O3/UV O3+H2OO2+H2O2
O3+H2O22·OH+O2
E-beam Electron accelerator H2O2.7·OH+0.6H++2.6 eq-
+0.45H2+0.7H2O2+H3O

P44
 2nd Stage: What ·OH does?
1) ·OH breaks double chains or aromatic (pollutants),
transforming toxic pollutants into biodegradable
compounds.
2) Oxidative agents continue reacting generating
water, carbon dioxide and inorganic salts.

P55
 AOP Applications

Main applications are:

• Landfills Leachate
treatment
• Recalcitrant or toxic
effluent from Industry
• Effluent organic matter
in biological treated
secondary effluent
• Drinking water

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 AOP Advantages and disadvantages
Advantages
Destroys toxic organic compounds
without pollution transfer to another
phase
Very efficient to treat almost all organic
pollutants and remove some toxic metals
Works also for water disinfection
Cheap to install
Disadvantages
Relatively high operation costs due to
chemicals and/or energy input.
Emerging technologies (still a lot of
research is required). Non full scale
experiences in some technologies.
Production of by-products, interfering
compounds and bromate formation (for
drinking water)
Safety is a key issue.
P77
 A full scaled process: OHP® Process
• Targets recalcitrant or toxic organic and
inorganic pollutants
• Based on Fenton Process
• Cyanides, Sulfides oxidation, Wastewater
disinfection
• BOD / COD Control (increase of
biodegradability)
• Mentioned in BAT Organic Fine Chemicals,
2006 (4.3.8.2) European Commission.
• Patented by PeroxyChem: “Method for Purifying
Waste Water”. EP1647529 B1. (2015)
• Methodology
• Lab Test
• Pilot Tests
• FEED and Detailed Engineering or EPC

P88
 OHP® Process

Continuous Process
Fully automated P99
 Control Process Parameters
• Temperature and Pressure
• Oxidant dosage (OHP ® reagent)
• Catalyst dosage (based in Iron and Cupper)
• Reactor(s) Residence Time
• Reactor Configuration
• (series, parallel)
• It is intrinsically safe.

Process Parameters are set to meet the client´s discharge

specifications and are determined in the OHP® Pilot Test
P1010
 Industries face the challenge of treating
recalcitrant and toxic organic pollutants
Contaminants Industries
• Oils and Hydrocarbons • Petrochemical / Refining
• Phenols
• Fine Chemicals
• Spent Caustics
• Polycyclic Aromatic Compounds (PAH)
• Pesticides
• Halogenated Organics (AOX)
• APIs
• Fine Chemicals
• Mercaptans
• Paint/Pigments
• Anylines and Pigments
• Pesticides • STW
• Cyanides • Landfills
• Sulphides
• PCBs
• Nitroaromatics
• Colorants AZO
• Clorobenzene
• Chlorinated Phenols
• Halogenated Aromatics in General
• Formaldehide 11
 Recalcitrant or Toxic Wastewater Pollutants
Treatment Technologies
OHP® fills the gap between
high P and T technologies and
Wet Air Oxidation
OHP® those effective at low COD
concentrations
COD (ppm)

There is no “concentrate”
generated with OHP®

Flow (m3/h) P1212

Wastewater Treatment Configuration with
OHP®

• Wastewater Pre-Treatment
• Biodegradability Enhancement

• Post-Treatment
• Polishing - EMC

• Standalone Treatment
• COD / TOC Elimination

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 OHP® – Benefits and Advantages
Effective for the reduction of organic matter (up to 99%).
Effective for biodegradability enhancement
Elimination of Specific compounds
Totally automated process.
Treatment of changing contamination conditions
Low maintenance costs
Open standard equipment.
High quality material selection
Easy and fast to start and stop
oved Technology –over 23 references in the market
P1414
 OHP® Biodegradability Increase examples
10000 4000
9000 3500
8000
3000
7000
4945 Hard COD BOD
6000 2500
DQO- DBO

2551 COD BOD

DQO - DBO
5000 2000
4000
1500
3000 1538
4255 1000
2000
1000 2412 500 1005
250
0 0 202
Before OHP After OHP Before OHP After OHP

Swiss Pharmaceutical Company in Leachate Industrial Waste Landfill

Spain
• Looking to improve performance of SBR
after initiating production of new products
• Dedicated to the production of generic drugs
and antibiotics (penicilin, azitromicin)
• Leachates typically have a very high
proportion of recalcitrant pollutants
• The treatment was designed to reach a
maximum COD of 500 ppm, or as
alternative a biological post-treatment P1515
 Biodegradability Increase with OHP® as
measured by the BOD:COD Ratio
Case Industry Pollutants After OHP Before OHP
Isocianates Nitrobenzoic acid,
Case 1 Manufacturer Nitro Amino cresols,
(German) Nitro Toluenes, Case 1

Petrochemical Spent caustics,

Case 2 Industry (various hydrocarbons, phenols, Case 2
wastewaters) etc

Antibiotics (penicilin,
Pharmaceuitical azitromicin) Case 3
Case 3 Manufacturer Bottom Distillation,
Mother Liquours

Hydrocarbons, oils, Case 4

MAPPOL
Case 4 Wastewater grease and other
(vessel rinse) organics
Case 5
Fungicides,
Fungicide pesticides
Case 5 Manufacturer
Case 6
Recalcitrant organics
Industrial Landfill from leachate
Case 6 from a Leachate 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

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 Specific Compounds Removal
• Pilot test run for a petrochemical Units are micrograms
company Pollutant Untreated Treated
• Target Elimination of specific compounds Metanol
Etanol
2,3 mg
62,8 mg
< 0,1
4
(priority pollutants) Isopropanol 2,5 mg < 0,1
Ac acetico 372 mg 50
• Chromatography performed to determine Ac propionico 36 mg 9
Ac butirico 221 mg 11
Priority Pollutants (IPPC EC) elimination Alcohol isoamilico 19 mg < 0.5
Benceno 846 < 0,1
• Operating Conditions Tolueno 616 < 0,1
• 115ºC Etilbenceno 561 < 0,1
• Xileno (p+m) 180 < 0,1
1,5 Barg
Estireno 307 < 0,1
• 0,5 % OHP Reagent Dibromoclorometano 3 < 0,1
• Cu, Fe based catalyst Tricloroetileno 1 < 0,1
• 1 hr residence time Bromodiclorometano 7 < 0,1
• 84,6% COD red. (CODi=350 ppm) Isopropilbenceno 3 < 0,1
Propilbenceno 4 < 0,1
1,3,5 TMB 3,6 < 1,1
terc-Butilbenceno 1,8 < 0,1
1,2,4 TMB 9,8 <1
Naftaleno 1800 < 0,1
Hidrocarburos pesados 12 < 0.3
P1717
 COD and TOC Reduction
OHP® Reagent vs TOC • Sample is a mix of mother liquors
Removal generated in pesticide production
• Wastewaters currently being treated by
incineration or evaporation
• Goal of treatment is incineration
substitution by eliminating TOC with
OHP®
• Process Conditions
• T=95ºC and P=1 Barg
• Catalyser is Fe and Cu based
• Successive additions of reagent
• RT is 60 min per stage

• Successfully removed pollutants

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 OHP® Technology – Methodology
Initial Meeting with Client:
determine if OHP® is appropriate Feasibility Test: at labs in Delfzijl
for application. Configuration. (Netherlands) or La Zaida (Spain)

Pilot Test: Pilot Plant

100 lt/h or 5 lt/h OHP® Plant
Engineering EPC – Start up
Process Guarantees

12 P1919
 OHP® Case Studies: 23 references all over the
world.
• Case I: Elimination of toxic, inhibitory and non biodegradable compounds
• Case II: Increase of Biodegradability of wastewater
• Case III: Elimination of TOC and COD in wastewater

Making OHP® plants since 1997

P2020
 Case Study I: OHP® for a Hazardous Waste
Facility
The company: Hazardous Waste Facility in Catalunya. They treat their customer’s
wastewater with Incineration, Evapo-Concentration, SBR, and a Physical-Chemical plant
including Chemical Oxidation. Wastewater from pharmaceuticals, fine Chemistry,
cosmetic, equipment cleaning, etc.

OHP® Objective: improve biodegradability of wastewater with soluble organic

pollutants and CODs up to 50,000 ppm. Organics are mostly recalcitrant nature
21 P 21
 Case Study I: OHP® for a Hazardous Waste
Facility
Process: highly variable flow 5 m3/h
 COD: between 5.000 and up to 50.000 ppm
 CODout < 800 ppm

Advantages:
 Reduces COD up to 90% to 95%
 Enhances biodegradability of wastewater so it can be treated downstream
 Saves cost by avoiding the use of more expensive processes

Installation: Low COD High COD

 Graphite Heat Exchanger Physical Chemical OHP® Evapo-Oxidation Incineration
 Glass-lined reactors
Biodegradable Non Biodegradable
 Final Physical Chemical step

Biological 22 P 22
 Case Study II: OHP® in API
The Company: API manufacturer for the Pharma
Industry. Strongly focused in sales to Generic
manufacturers in USA and Europe
Situation: in 2003, existing SBR system could not
absorb increased production of new products
manufacturing due to its WW of recalcitrant nature,
biocides and biological inhibiting material content .
 Alternative was offsite treatment of hard COD streams
at high important cost. Ozone treatment was tested as
well without satisfactory results
Generics Generics  Highly variable and seasonal wastewaters added to
USA/Canada Europe complexity of the situation
APIs Produced

Contract Generics
Manufacturing Worldwide
P2323
Commodities
 Case Study II: OHP® in API
OHP® Objective: enhance biodegradability of the hard-COD wastewater streams
Advantages:
 Increase capacity of wastewater treatment system (almost doubled capacity)
 Achieve cost savings by substituting offsite treatment for OHP ®
Installation: many works had to be completed to segregate hard COD streams
 1 Glass lined reactor
 Hastelloy C heat exchangers and economizer
 Final Physical-chemical step, including a filter press for sludge dewatering

COD = 150.000
Wastewater Q=5 Off site
Treatment
Separation Treated
COD = 6.400
Wastewater
Phisico-Chemical Biological
Q = 300 COD = 900 Treatment Process
Q = 295 COD = 700 COD = 500
Yield. = 1,22 Q = 245 Yield. = 1,42 Q = 295

COD = 17.000 COD = 7.500

Q = 50 Q = 50
OHP® P2424
Rto. = 2,31
 Case Study III: OHP® for landfill’s leachate treatment
The Company: Municipal solid waste facility including municipal waste recycling,
urban waste landfill, composting and solar power generation.
Situation: in year 2003, large volume of leachate generated to be discharged to the local
Municipal STW. Recalcitrant nature of leachate and ammonia content obliges the
company to install an advanced technology for wastewater treatment
 Wastewater originated in landfill leachate and composting
 Reverse osmosis, Biological and Physico-Chemical were the technologies evaluated

P2525
 Case Study III: OHP® for landfill’s leachate treatment
OHP® Objective:
flow = 4 m3/h
Anoxic liquid, rich in organic acids and sulphates
 Avg. COD is 7,000 with max. 14,000 ppm
 Design Discharge COD spec is 1,500 ppm
 Ammonia < 50 ppm

As of 2009:
Avg. COD Leachate: 4.000 to 6.000 ppm
Avg. COD discharge: 400 to 500 ppm
Advantages:
 Flexibility to treat leachate with changing
characteristics and variable volume flow
 Removes hard COD and Ammonia in one unit
 Spent catalyst can be disposed in same landfill

Installation:
 One 6 m3 glass lined reactor
 Heated with Heating Oil
 Final Phisico Chemical step
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 Summary of the session
We have covered:
 What AOP is?
 Summary of AOP
 Application, advantages and disadvantages
 OHP® Technology
 Case Studies
Elena Gil Aunon Msc, Bsc (Hons)
Associate Director, Infrastructure,
Amec Foster Wheeler Environment & Infrastructure UK Limited
4th Floor, 60 London Wall, London EC2M 5TQ United Kingdom
M +44 (0)7793454627
elena.gilaunon@amecfw.com      amecfw.com

  Jacobo Villagran:
jacobo.villagran@peroxychem.com
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