pharmaceutical waste water

1. 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

2. contents
1. Overview of industries
2. Parameters
3. Recovery process
4. Treatment technology
5. Conclusion

3. Overview…..
Pharmaceutical
Company
Chemical Synthesis
Cardiovascular
agents,
antihistamines , CNS
stimulants etc.
Fermentation Plants
Steroids,
therapeutic
nutrients, vitamins
Formulation Plants
Tablet, topical,
syrup, injectables,
sterile
manufacturing,
Natural/Biological
product Extraction.
Vitamins,
antibiotics, enzymes
etc.

4. 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.

5. 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.

6. 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.

7. Untreated water discharged

8. Parameters??
How to know the toxicity of water??

9. Parameters
Parameters Permissible limits Actual measures of samples
collected from pharmaceutical
industry wastewater
Chemical Oxygen Demand
(COD)
200mg/L 1500mg/L-7000mg/L
Biological Oxygen Demand
(BOD)
30mg/L-50mg/L 950mg/L-4000mg/L
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

10. Treatment by
different
process
Recovery
Hybrid
Technologies
How to get rid of this waste
generated

11. Treatment by different process

12. Biological
treatment
Aerobic
• Activated
Sludge
• Membrane
Bioreactors
Anaerobic
Advanced
Treatment
Membrane
technology
Activated
carbon
Rotating
Biological
contactors
Membrane
distillation
Advanced
Oxidation
technique
Ozone/Hydroge
n peroxide
treatment
Fenton’s
oxidation
treatment
Wet air
oxidation
Ultrasound
irradiation
Electrochemica
l oxidation/deg
Photo catalysis
Hybrid
technologies
For
Fermentatio
n Process
For Chemical
Synthesis
Process
Treatment of Pharmaceutical wastewater & Recovery of
valuable or complex compounds

13. 1. Biological Treatment
 Conventional
 Aerobic and Anaerobic treatment
 Microorganisms help in degradation of waste
 Reliable
 Sludge can
be reused

14. 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.

15. 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
present in waste
stream
i. Analgesics & Anti-
inflammatory
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

16. 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:

17. Study 1 Study 2 Study 3 Study 4
Compounds APIs Tylosin,
antibiotic
Vitamin Chemical
synthesis water
temperature 55°C High temp. - -
Pre-treatment 9kg
COD/(m³.d
ay)
- 70000mg/L-
120000mg/L
COD
40000mg/L-
60000mg/L
COD
Post-treatment 70% COD
removal &
85% BOD
75% COD &
95% tylosin
removal
95% COD
removal
70% removal

18. Basic Diagram for USAR :

19. 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

21. Recovery processes

22. 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
technology
Carbon
Adsorption
Membrane
Distillation

23. 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%

24. 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).

25. PAC
 It is freshly prepared.
 It showed adsorption of 62
EDCs.
 It was capable of partially
removing all target
compounds depending on
physio-chemical
properties.
GAC
 It is usually recycled in
fixed bed columns.
 Series of GAC columns
removed 99% of total
mercury & 90% copper.
 96% phenol removal

26. 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.

27. Advance
d
Oxidatio
n
treatmen
t
Ozone/
Hydrogen
Peroxide
Treatment
Fenton’s
Oxidation
treatment
Wet Air
Oxidation
Electro-
chemical
Oxidation/
Degradatio
n
Photo
catalysis
Ultrasoun
d
Irradiation

28. 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.

29. Process Flow

30. 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.

31. Process Diagram for the Fenton’s
Oxidation

32. 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.

33. Process diagram

34. 4. Electro chemical
Oxidation/Degradation
 E° = 2.8V
 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.
˙OH/H O
2

35. Process diagram

36. 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.

38. 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

39. Ultrasound coupled with UV
treatment

40. Hybrid
Technology
For Chemical
Synthesis
Process
For
Fermentation
Process

41. What is hybrid technology?
 Combining different technologies together .
 Efficient method
 Better output

42. 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:
TDS 8500-9000mg/L
TSS 2800-3000mg/L
COD 13000-
15000mg/L
BOD 7000-7500mg/L
BOD:COD 0.45-0.6
Pre-treatment
COD 65%-75%
BOD 80%-90%
Post-treatment
The process has high biomass
production rate thus making the
process economically feasible

44. 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
treatment
Fenton oxidation &
aerobic treatment
Primary treatment tech.
used in hybrid process
Ozonation Fenton Oxidation
Secondary treatment
tech. used in hybrid
process
Aerobic (i.e. Membrane
Bioreactor Tech.)
Aerobic biological
degradation
Removal >90% COD & TSS 98% COD

45. Process Flow
Influent to
ETP
Primary
treatment (
generally AOPs
)
Secondary
treatment (
generally
biological
degradation )
Treated water
is discharged
from the ETP

46. 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

47. 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’.

48. Thank you!!