Pharmaceutical

Waste-Water
Presented by,
Parth Naik
ICT, Mumbai

Under guidance of,

Dr. S. P. Kamble
Scientist,
Chemical Engineering & Process
Development Division,
National Chemical Laboratory,
Pune
contents

1. Overview of industries

2. Parameters

3. Recovery process

4. Treatment technology

5. Conclusion
 Overview…..

Pharmaceutical
Company

Natural/Biological
Chemical Synthesis Fermentation Plants Formulation Plants product Extraction.

Cardiovascular Tablet, topical,

Steroids, Vitamins,
agents, syrup, injectables,
therapeutic antibiotics, enzymes
antihistamines , CNS sterile
nutrients, vitamins etc.
stimulants etc. manufacturing,
What is it?
 Waste generated after washing reactors, process lines.

 Constitutes of solvents, Active Pharmaceutical

Ingredients (API), detergents, catalysts etc.

This increases the toxicity of waste

water and makes it unfit for the

survival of aquatic life and, also

incompetent for our use.

From where does it
originates?

Cleaning of reaction vessels.

 Cleaning of shop floors.
 Sewer leakages, accidental spills.
Unpermitted dumping.
 Metabolites or few APIs which doesn’t get
degrade easily.
What are its effect on
Environment?
 They have intrinsic biological activity which may lead to fatal
outcomes.

 It leads to development of antibiotic resistant microbes.

 Retardation in methanogenesis.

 Endocrine disrupting compounds (EDCs) are tend to disrupt

human endocrine system.

 Recent studies have shown that pharmaceutical products in

water streams can lead to feminization in fishes.

 Diclofenac was found to direct cause of vulture population in

India.

 Disturbs biosphere and eco-system.

Untreated water discharged
How to know the toxicity of water??

Parameters??
 Parameters
Parameters Permissible limits Actual measures of samples
collected from pharmaceutical
industry wastewater
Chemical Oxygen Demand 200mg/L 1500mg/L-7000mg/L
(COD)

Biological Oxygen Demand 30mg/L-50mg/L 950mg/L-4000mg/L

(BOD)

Total Suspended Solids (TSS) 10mg/L 60mg/L-650mg/L

Total Dissolved Solids (TDS) 1500mg/L 1400mg/L-7500mg/L

pH 6.5-8 2-9

Oil & Grease 10mg/L 50mg/L-12000mg/L

How to get rid of this waste
generated

Treatment by
different Hybrid
Technologies Recovery
process
Treatment by different process
Treatment of Pharmaceutical wastewater & Recovery of
valuable or complex compounds

Advanced
Biological Advanced Hybrid
Oxidation
treatment Treatment technologies
technique
Ozone/Hydroge
Aerobic Membrane n peroxide
treatment
• Activated technology
For Chemical
Sludge Fenton’s
oxidation Synthesis
• Membrane Activated treatment Process
Bioreactors carbon
Photo catalysis
Rotating
Wet air
Biological oxidation
contactors For
Anaerobic Electrochemica Fermentatio
l oxidation/deg n Process
Membrane
distillation Ultrasound
irradiation
1. Biological Treatment
 Conventional

 Aerobic and Anaerobic treatment

 Microorganisms help in degradation of waste

 Reliable

 Sludge can

be reused
a) Aerobic
 In presence of air
 Generates
i. Activated Sludge (AS)
 AS efficiency
depends mainly
on temperature and
hydraulic retention
time (HRT).
 A study revealed that
nitrogen removal can be
achieved up to 99% and
high degree of removal
efficiency of Ibuprofen,
Naproxen, Ethlynilestradiol etc.
but drugs such as Sulfomethaxazole,
Diclofenac were resistant to this.
 ii. Membrane bioreactor
• Technically and economically
feasible alternative for water
treatment.
• It has high sludge retention time
within compact reactor volume.
• Concentration of micro organisms
can reach up to 20mg/L ; this
increases the degradation capacity
of larger organic molecules.
Compounds i. Analgesics & Anti-
present in waste inflammatory
stream ii. fermentation process
Pre-treatment i. – n.a
ii. 40000mg/L COD

Post-treatment i. 98.7% TSS & 90.4%

total COD removal.
ii. >90% COD & >98%
BOD
b) Anaerobic
 In absence of air.

 Biogas is by-product.

 Fluidized bed reactors, up-flow anaerobic sludge reactors(USAR)

etc. are used .

 Anaerobic hybrid reactors are specialized forms which have

suspended and attached growth combined.

 Anaerobic can deal high conc. wastewater when compared to

aerobic systems, giving economical by-product, low sludge yield,
low operating cost, less energy inputs.

 A study revealed following results for USAR:

 Study 1 Study 2 Study 3 Study 4

Compounds APIs Tylosin, Vitamin Chemical

antibiotic synthesis water

temperature 55°C High temp. - -

Pre-treatment 9kg - 70000mg/L- 40000mg/L-

COD/(m³.d 120000mg/L 60000mg/L
ay) COD COD

Post-treatment 70% COD 75% COD & 95% COD 70% removal
removal & 95% tylosin removal
85% BOD removal
Basic Diagram for USAR :
Rotating Biological Contactors

 Consists of disks mounted on a shaft which are partially submerged in

wastewater and the other half is in exposed to air.

 Interfacial surface area in more.

 Rotation speed is ( 1-10 rpm ).

 Thin film formed over the shell helps in better aeration.

 A study shows good removal efficiency of COD.

 800mg/L COD influent and it showed 60% removal efficiencies

Recovery processes
Advanced treatment Process
 It is primary treatment.
 Enhances the removal efficiency of secondary
treatment.
 Helps in recovering valuable products after washing or
cleaning of reaction vessels.
Advanced
treatment
process

Membrane Carbon Membrane

technology Adsorption Distillation
 Membrane Technology
 It is used for recovery.
 Generally, the molecular weights are used as the basis.
 Nanofiltration
 Ultra filtration
 Reverse Osmosis

Reverse Osmosis 95% recovery of amoxicillin

Nano filtration >97% recovery of amoxicillin & >40%
rejection of COD
permeation flux 1.5L/(min.m²)
Ultra filtration Alkaline protease recovery 83%
 Activated Carbon

 It is suitable for adsorption of

many organic compounds.

 It has high surface area (over

1000m²/g).

 This process uses powered

activated carbon (PAC) or
granular activated carbon
(GAC).
PAC GAC

 It is freshly prepared.  It is usually recycled in

fixed bed columns.
 It showed adsorption of 62
 Series of GAC columns
EDCs.
removed 99% of total
 It was capable of partially mercury & 90% copper.
removing all target
 96% phenol removal
compounds depending on

physio-chemical

properties.
 Membrane Distillation

 Presently it is used for demineralization of water.

 It operates at atmospheric conditions, heat requirement

is low.

 It has been successfully applied for recovery of acids

from fermentation broth.

 Membrane fouling is a major disadvantage.

 Ozone/
Hydrogen
Peroxide
Treatment
Fenton’s
Ultrasoun Oxidation
d treatment
Irradiation Advance
d
Oxidatio
n
treatmen
t Wet Air
Photo Oxidation
catalysis
Electro-
chemical
Oxidation/
Degradatio
n
 1. Ozone/Hydrogen Peroxide
Treatment
Ozone decomposes in water to form hydroxyl radicals
which is stronger oxidizing agent compared to ozone .

A study on COD removal was carried out.

In presence of hydrogen peroxide
decomposition of ozone is rapid and
the COD removal efficiency was
enhanced by 76%.

Amide linkages are quite resistant to

ozonation.
Process Flow
 2. Fenton’s Oxidation
Iron acts as a catalyst.
It is a heterogeneous catalytic reaction.

A study on COD and API removal efficiency was analyzed based on

Fenton Chemistry :

More than 95% COD removal was observed

in a pharmaceutical effluent containing Chloramphenicol,
Paracetamol & COD ̴ 12000mg/L.

Penicillin was completely eliminated after 40

min of advanced oxidation with Fenton/UV treatment.

pH ranges from 3 – 4.
Process Diagram for the Fenton’s
Oxidation
 3. Photo catalysis
 It is best suited for effluents having
high COD.

 Photo catalytic reactions obey the

Langmuir-Hinshelwood kinetic
model which is reduced to pseudo-
first order or zero-order kinetics
depending on operating condition

 A novel semiconductor photo

catalysis by using a combination of
TiO2 with RuO2-IrO2 as anode and
chloride as an electrolyte has also
shown 95% COD.
Process diagram
 4. Electro chemical
Oxidation/Degradation
 E° = 2.8V
˙OH/H O
2

 An experimental data showed good results with this technique.

 Stimulated waste consisting Paracetamol & Diclofenac showed

more than 97% TOC removal by a boron doped diamond (BDD)
anode.

 Rate is dependent on BOD conc. and electrode thickness.

 Electro coagulation when coupled with photo catalysis showed

86% COD removal of chemical synthesis wastewater.
Process diagram
 5. Wet air oxidation
Thermo chemical process where hydroxyl radicals and other active
oxygen species are formed at elevated temperatures (200°C–
320°C) and pressures (2-20 MPa). Recent research showed
applicability of this process to remove COD. Catalytic wet air
oxidation of a chemical synthesis wastewater having COD of 7-
12g/L showed removal of total organic matter and the process
enhanced with enhanced loading of heterogeneous Cu catalyst
and high temperature.

This process can be used as pre-treatment process thereby making

the waste water suitable for biological treatment.
 6. Ultrasound Irradiation
 New technique

 High intensity acoustic irradiation with frequencies that

produce cavitations (25kHz)

 Many EDCs been removed from contaminated water,

reduction of 80-90% COD within 40-60min.

 Best suited for treatment of two-phase waste water.

 When coupled with UV treatment resulted in >90% of

Clofibric acid & >98% of Carbamazepine, Diclofenac
Ultrasound coupled with UV
treatment
 Hybrid
Technology

For Chemical For

Synthesis Fermentation
Process Process
What is hybrid technology?

 Combining different technologies together .

 Efficient method

 Better output
 For Chemical Synthesis Process
 It usually contains high conc. of organics (reagents,
intermediates, final product).
 A study on hybrid up-flow anaerobic sludge blanket reactor
having following measured values:

Pre-treatment Post-treatment

TDS 8500-9000mg/L COD 65%-75%

TSS 2800-3000mg/L BOD 80%-90%
COD 13000-
15000mg/L The process has high biomass
BOD 7000-7500mg/L
production rate thus making the
process economically feasible
BOD:COD 0.45-0.6
 For Fermentation Process
 Generally consists of fermentation broth, mycelia, and
nutrients for cell cultivation.

 Organic solvents for recovery of API.

Study 1 Study 2
Contaminants Estrogens Iodine, organic comp.
metal salts
Treatments used Ozonation & Aerobic Fenton oxidation &
treatment aerobic treatment
Primary treatment tech. Ozonation Fenton Oxidation
used in hybrid process
Secondary treatment Aerobic (i.e. Membrane Aerobic biological
tech. used in hybrid Bioreactor Tech.) degradation
process
Removal >90% COD & TSS 98% COD
Process Flow
Primary Secondary
treatment ( treatment (
generally AOPs generally
) biological
degradation )

Influent to
ETP Treated water
is discharged
from the ETP
What to do now?
 Reduction of waste at the source.

 Recycling of water.

 Using filtration techniques to recover complex

compounds.

 Increased membrane processes to recover valuable

products based on the molecular size.

 Application of recovery process at the source of

pollutant generation by deeply understanding the
stages
Conclusion
 Pharmaceutical industries require good quality of water
feed but in return the discharged water is of bad quality.
 Enter into the nature through usage and inappropriate
disposal from manufacturing location.
 Disturbing the biosphere (because of EDCs ).
 Use of hybrid technology for removal of recalcitrant
compounds.
 Membrane bioreactor is a promising solution.
 Anaerobic reactors are employed on a wide scale as the
by-product i.e. bio-gas can be economically used, along
with the sludge generated by agriculture industry.
 Most technologies are ‘removal’.
 Emphasis is and should be on ‘recovery’.
Thank you!!