Wastewater Characteristics in the Pharmaceutical Industry
- 1. Wastewater Characteristics in the Pharmaceutical Industry Presented by Tanvir Siddike Moin Submitted to Dr. Rowshan Mamtaz Professor DEPARTMENT OF CIVIL ENGINEERING BUET
- 2. Water for Pharmaceutic al Use • Pharmaceutical water includes different types of water used in the manufacture of drug products • THE 8 TYPES OF WATER ARE: • Non-potable • Potable (drinkable) water • USP purified water (United States Pharmacopeia) • USP water for injection (WFI) • USP sterile water for injection • LUSP sterile water for inhalation • USP bacteriostatic water for injection • USP sterile water for irrigation
- 3. Water Quality • The USP designation means that the water is subject to an official monograph by the US Pharmacopeia. • There are four different kinds of specifications for water, and these four have different functions. • Potable Water is generally gathered from municipal water systems or from a natural water source. Serial Parameter Potable Water Purified Water Water for Injection Sterile Water for Injection 1 Appearance Clear, colorless, and no visible particles Clear, colorless, and no visible particles Clear and colorless Clear and colorless 2 Odor Odorless Odorless Odorless Odorless 3 pH 6.5-8.5 5.0-7.0 5.0-7.0 5.0-7.0 4 Chloride NMT 250 ppm 0 ppm 0 ppm 0 ppm 5 Aluminum 0.2 mg/L 0 mg/L 0 mg/L 0 mg/L 6 Arsenic 0.01 mg/L 0 mg/L 0 mg/L 0 mg/L 7 Fluoride 1.5 mg/L 0 mg/L 0 mg/L 0 mg/L 8 Boron 0.3 mg/L 0.3 mg/L 0 mg/L 0 mg/L 9 Sulfate NMT 300 ppm 0 ppm 0 ppm 0 ppm 10 Total hardness NMT 500 ppm 0 ppm 0 ppm 0 ppm 11 Microbial count 500 cfu/ml 100 cfu/ml 10 cfu/ml 10 cfu/ml 12 Acidity or Alkalinity - NMT 0.1 ml of 0.01M NaOH NMT 0.1 ml of 0.01M NaOH NMT 0.1 ml of 0.01M NaOH 13 Ammonia 0.5 ppm 0.2 ppm 0 ppm 0 ppm 14 Heavy Metals 0.5 ppm 0.1 ppm 0 ppm 0.1 ppm 15 Conductivity NMT 0.3 µs NMT 0.1 µs NMT 0.1 µs NMT 0.05 µs • Pharmaceutical waste poses its own set of unique problems. • Since it contains certain pharmaceutical chemicals, the wastewater must be treated in specific ways before it can be released. INTRODUCTION
- 4. Wastewater Characterization Mixing, compounding and formulation • May contain carbohydrates and inert formulating material Low to moderate in BOD • Low TSS • Around neutral pH Fermentation • Mycelium cake - wet cake has 40-70 g/l of BOD and 30-50 g/1 of TSS • BOD-2500-1000 mg/1 • pH-4-8 Vaccination, microbial suspension, antitoxin preparation • Wastes contain very high BOD/COD and bad odours • Antiseptic and anti-bacterial agents contribute to toxicity Chemical synthesis • General process liquor High strength process liquor Acidic and alkaline effluent • Emulsified effluent • Toxic effluent
- 5. Maximum Allowable Concentration of Toxic Substances Toxic Substances Maximum Allowable Concentration (mg/L) Lead (Pb) 0.05 Selenium (Se) 0.01 Arsenic (As) 0.05 Chromium (Cr) 0.05 Cyanide (CN) 0.2 Khan Associates, (2006)
- 7. Characteristics Of Wastewater Generated From Pharmaceutical Process Parameter Concentration (mg/L) pH 6.65-7.40 Total Alkalinity 1800-2100 TDS 15500-16700 VS 6400-6600 SS 9150-9240 COD 23700-24500 BOD5 11500-12100 Chlorides 3900-4100 Sulphates 400-650 Phosphates <98 Khan Associates, (2006)
- 8. Characteristics Of Liquid Waste Of NAVANA Pharmaceutical Ltd. Khan Associates, (2006)
- 10. Total Water 4180 m3/day Utilities 1700m3 Boiler 400m3 Regeneration 50m3 Cooling Tower 1250m3 Process 1450m3 Services 900m3 ETP Chemical Preparation 10m3 Others 50m3 Gardening 70 m3 ETP Treatment Plant 12888 m3/day 1378 m3 850 m3 10 m3 360 m3 50 m3 240 m3 Water Balance For A Fermentation Process For A Manufacturing Plant Producing Penicillin Khan Associates, (2006)
- 11. Water Balance For A Fermentation Process For A Manufacturing Plant Producing Paracetamol Khan Associates, (2006)
- 12. 1. Spent Liquors 2. Chemical Waste 3. Condenser Waste 4. Washing Waste Water parameters in the inlet and outlet in sample company Wastewater Treatment • The wastewater treatment process varies with the company and the type of drug produced. • Since there are no universal regulations in Bangladesh, a sample company’s treatment system, NAVANA Pharmaceuticals Ltd, was used to give an idea of what is done. Common Wastewater Components Khan Associates, (2006)
- 13. • Diverse characteristics of PWW. Different medicines produce different type of waste Variable amount of products • Mixing of pharmaceutical waste with other type of waste • Also, it may contain high BOD and highly variable pH • Halogenated/non-halogenated solvents • Organic chemical residues from still bottom Sludge & tars • Heavy metals • Test animal remains • Return pharmaceuticals Low-level radioactive waste • Contaminated filters, etc. Types of Waste PROBLEMS INVOLVED IN PHARMACEUTICAL WASTEWATER TREATMENT
- 14. Treatment Methods View of Existing ETP Chemical Treatment • After aerating the effluent, it is transferred into a reaction tank. Here, chemical treatment takes place. • An optimum number of flocculants are used to generate floc. • This floc is allowed to settle at the bottom, where it becomes the sludge from the primary clarifier. • This is pumped off. Primary Treatment Physical Treatment • In this step, as with ordinary primary treatment, a screening process takes place. • The wastewater passes through a screen chamber to get rid of any large suspension material. • Then it is deoiled using oil and grease. Afterward, it is drained into an equalization chamber. • This equalization chamber is kept aerated using a diffused air flow system.
- 15. • Secondary Treatment • Biological Treatment • The clarified effluent is then transferred to a biological treatment chamber. • It is then aerated again. • This allows for aerobic biological reactions to occur. • Organic matter that is dissolved in it is digested. • Sludge Treatment • Sludge is taken from both primary and secondary clarifiers. • This sludge is then dried in a drying bed. • After over six months, the sludge is dumped in a landfill. • Generally, the client offers storage and disposal systems for the sludge produced in the manufacture of their order. • • Effluent Disposal • In Bangladesh, there are no proper disposal systems in place. • Thus, after treatment of the water, it is released into a nearby canal or river. • Solid Waste • There is a good amount of solid waste produced as well. • Generally solid waste consists of heavy metals, test animal remains, contaminated filters, among others. • In Bangladesh, again, unfortunately, there are no specified methods.
- 17. QUANTITIES GENERATED In Ireland about 43 tons of BOD produced per day from Pharmaceutical Industry. In USA during 1983, about 3 million tons of hazardous waste produced in which 200,000 tons of sludge produced by pharmaceutical industry only. In India out of 960 million tons of solid waste, about 2 million tons comes fro herbal and agricultural industry. Unfortunately, Bangladesh has no formal estimate of pharmaceutical waste. Companies keep a record of their own wastes, but that information is often confidential. Thus, the information of NAVANA Pharmaceuticals Ltd was used as the sample industry.
- 18. Secondary Clarifier of Existing ETP Based on pressure application • Removal of dissolved solids • Depends on concentration and pH In the reverse osmosis process cellophane-like membranes separate purified water from contaminated water. • RO is when a pressure is applied to the concentrated side of the membrane forcing purified water into the dilute side, the rejected impurities from the concentrated side being washed away in the reject water. • RO can also act as an ultra-filter removing particles such as some micro-organisms that may be too large to pass through the pores of the membrane Physical Treatment 1. Reverse osmosis (RO): Primary Clarifier of Existing ETP
- 19. When a concentrated salt solution and pure water are separated by a semipermeable membrane, pure water will move across the membrane to dilute the salt water until the salt concentration is equal on both sides of the membrane, in a process called osmosis. If enough pressure is exerted on the concentrated solution to overcome osmosis, reverse osmosis occurs. Pure water is forced out of the concentrated solution. Osmosis Reverse Osmosis Physical Treatment
- 20. Based on the chemical activity of the solute • Recovery of specific material from aqueous solution • depends on the molecular weigh and dialysis coefficient Based on the application of an electric field Used to separate ionized species • Operates over a wide range of pH • Electrodialysis Membrane System works to achieve separation on the ionic components of the water using semi-permeable membranes. 2.Dialysis: Electrodialysis: Sludge holding tank and drying bed of Existing ETP Electrodialysis cell Physical Treatment
- 21. • Cation-selective membranes consist of sulphonated polystyrene, while anion-selective membranes consist of polystyrene with quaternary ammonia. • Sometimes pre-treatment is necessary before the electro dialysis can take place. • Suspended solids with a diameter that exceeds 10 μm need to be removed, or else they will plug the membrane pores. • There are also substances that can neutralize a membrane, such as large organic anions, colloids, iron oxides and manganese oxide. • These disturb the selective effect of the membrane. This technique can be applied to remove ions from water. Particles that do not carry an electrical charge are not removed. Granular Activated Carbon Adsorption: • Used for removal of organic contaminants (COD) • The survey showed that 1 out of 25 pharmaceutical plants use this method to treat their wastewater, • COD tests nearly all organic compounds can be fully oxidized to carbon dioxide with a strong oxidizing agent under acidic conditions Physical Treatment
- 22. Filtration: Used to remove particulate contaminants Colloidal suspensions of fine solids may be removed by filtration through fine physical barriers distinguished from coarser screens or sieves by the ability to remove particles smaller than the openings through which the water passes. Sedimentation: • Suspended particles are allowed to settle and the supernatant is removed. • Solids and non-polar liquids may be removed from wastewater by gravity when density differences are sufficient to overcome dispersion by turbulence. Flocculation: • Gathering of fine particles as flocculates which allows them to settle. • It is a process wherein colloids come out of suspension in the form of floc or flake; either spontaneously or due to the addition of a clarifying agent. Physical Treatment
- 23. Steam Stripping : • Differences in relative volatility between the organic chemicals and water are used to achieve a separation Used for the recovery of solvents • Steam stripping, also known as steam distillation, is an economic method of cleaning up plant wastewater streams. • It is a multistage continuous distillation process where steam is used as a stripping gas to remove hydrocarbons from dischargeable waste waters;
- 24. Chemical Treatment Neutralization: A process utilized to prevent excessively acidic or alkaline wastes discharge 1 out of 2 pharmaceutical plants use neutralization to treat their wastewater Ion-exchange: ■ Reversible interchange of ions between a solid and a liquid phase ■ Used for the removal of trace metals, fluorides, nitrates, and manganese ■ Ion exchange is an exchange of ions between two electrolytes or between an electrolyte solution and a complex. Figure: Acidic and Alkaline Wastewaters Neutralize Each Other
- 25. Reduction: Treatment with sulphur dioxide to reduce the oxidants to less noxious materials Precipitin: Separation of solid from aqueous waste chemically Calcination: Heating waste to a high temperature to oxidize organic matter Effluent From Production Area Screening Chamber Raw Effluent Tank Oil & Grease Separation Equilization Flocculation Flush Mixer Primary Clarification Liquid Waste Sludge Holding Tank Sludge Drying Bed Reference: INCEPTA Company Chemical Treatment
- 26. Incineration: • Controlled heating processes to covert a waste to less bulky, less toxic or less noxious • Incineration usually involves the combustion of unprepared (raw or residual) • To allow the combustion to take place enough oxygen is required to fully oxidize the fuel. • Typically, incineration plant combustion (flame) temperatures are in excess of 850°C and the waste is converted into carbon dioxide and water. Pyrolysis: • Thermal decomposition of waste at high temperatures in the absence of oxygen • Pyrolysis is the thermal degradation of a substance in the absence of oxygen. • This process requires an external heat source to maintain the temperature required. • Typically, relatively low temperatures of between 300°C to 850°C are used during the pyrolysis of materials such as MSW. • The products produced from pyrolyzing materials are solid residue and synthetic gas (syngas). Thermal Treatment
- 27. • Used to remove biodegradable organic matter • Microorganisms convert organics into: CO, and H2O (aerobic) CO2, CH4, and H2O (anaerobic) • 1 out of 3 pharmaceutical plants uses biological processes Biological Processes Activated Sludge: • process in which microorganisms are continuously circulated and contacted with organic waste in the presence of oxygen • Sludge withdrawn from the secondary clarifier in the activated sludge process, consisting of micro- organisms, non-living organic matter, and inorganic materials. Biological Treatment Liquid Waste Moving Bed Biological Reactor 1 Secondary Clarification 1 Moving Bed Biological Reactor 2 Secondary Clarification 2 PSF PUMP Sand Filter Activated Carbon Filter Water Tank 1 Activated Carbon Filter Water Tank 2 Liquid Discharge to Environment Reference: INCEPTA Company
- 28. An activated sludge process includes: • An aeration tank where air (or oxygen) is injected and thoroughly mixed into the wastewater. • A settling tank (usually referred to as a clarifier or "settler") to allow the waste sludge to settle. • Part of the waste sludge is recycled to the aeration tank and the remaining waste sludge is removed for further treatment and ultimate disposal Biological Treatment
- 29. Aerated Lagoons: A basin in which organic waste is stabilized by a dispersed biological growth in the presence of oxygen promotes the biological oxidation of wastewater. Types Of Aerated Lagoons Or Basins • Suspension mixed lagoons, where there is less energy provided by the aeration equipment to keep the sludge in suspension. • Facultative lagoons, where there is insufficient energy provided by the aeration equipment to keep the sludge in suspension and solids settle to the lagoon floor. • The biodegradable solids in the settled sludge then degrade anaerobically. Biological Treatment
- 30. Waste Stabilization Ponds (Polishing ponds) • Waste or Wastewater Stabilization Ponds (WSPs) are large, man-made water bodies in which blackwater, greywater or fecal sludge are treated by naturally occurring processes and the influence of solar light, wind, microorganisms and algae. • The ponds can be used individually or linked in a series for improved treatment. There are three types of ponds: 1. anaerobic, 2. facultative and 3. aerobic (maturation), • Anaerobic digestion is a collection of processes by which microorganisms break down biodegradable material in the absence of oxygen • Closed tanks operated in the absence of oxygen • In this method, large fraction of organic matter is broken down into carbon dioxide and methane and is accomplished in the absence of oxygen. Anaerobic Digestion Biological Treatment
- 31. • Artificial beds of rocks or other porous media through which aqueous organic waste percolated and brought into contact with biological growth and oxygen • A trickling filter consists of a bed of rocks, gravel, slag, peat moss, or plastic media over which wastewater flows downward and contacts a layer (or film) of microbial slime covering the bed media. • Aerobic conditions are maintained by forced air flowing through the bed or by natural convection of air. • The process involves adsorption of organic compounds in the wastewater by the microbial slime layer, diffusion of air into the slime layer to provide the oxygen required for the biochemical oxidation of the organic compounds. • The end products include carbon dioxide gas, water and other products of the oxidation Trickling Filters Biological Treatment Ref:Wikipedia
- 32. ANAEROBIC TREATMENT Commonly Used Anaerobic Systems 1. Up-flow filters 2. Membrane reactors 3. Continuously-stirred reactors 4. Fluidized bed reactors Anaerobic treatment of pharmaceutical waste is common in different countries because of 1. lack of biodegradability 2. toxic and 3. malodorous nature of pharmaceutical waste Biological Treatment Ref:Wikipedia
- 33. ANAEROBIC TREATMENT • The anaerobic filter is ideally suited for the treatment of soluble wastes. • No effluent or solids recycling is required with the anaerobic filter because biological solids remain in the filter and are not lost with the effluent. • The accumulation of high concentrations of active solids in the filter permits the treatment of dilute wastes. • Very low volumes of sludge are produced. • Effluent is essentially free of SS. • Anaerobic filter giving 70-80%. COD removal efficiency and 94% BOD, the removal efficiency • It gives 33% better performance as compared to the aerobic extended aeration system • Very low volumes of sludge produce • Remove color with higher efficiency
- 34. Treatment or Disposal • There is not much treatment of solid pharmaceutical waste. • Most of the time solid waste is disposed of. Methods of Waste Disposal 1. Landfills 2. Incineration 3. Source reduction 4. Composting 5. Recycling LANDFILLS • Landfills are physical facilities used for the disposal of residual solid wastes in the surface soils of the earth • US. EPA defines a landfill as a system designed and constructed to contain discarded waste to minimize releases of contaminants to the environment • Solid pharmaceutical waste is usually incinerated but, in some places, (e.g California) most of the solid PW is landfilled Waste Disposal LANDFILLS Ref:Wikipedia
- 35. Incineration • combustion of solid waste • Solves space problem but: produces toxic gases like CI, HCI, HCN, SO, • High temp furnaces break down hazardous compounds but are expensive • Heat generated can be recovered Source Reduction • Most fundamental method of reducing waste is to prevent it from being produced • Reduce and reuse 1. Saves natural resources. 2. Reduces waste toxicity 3. Reduces costs Composting • Harnessing natural decomposition to transform organic material into compost • Composting is the biological decomposition of organic waste such as food or plant material by bacteria, fungi, worms and other organisms under controlled aerobic (occurring in the presence of oxygen) conditions. Waste Disposal
- 36. RECYCLING SOLID WASTE • Recycling is a process to convert waste materials into new products to prevent: • waste of potentially useful materials, • reduce the consumption of fresh raw materials, • reduce energy usage, • reduce air pollution (from incineration) and • water pollution (from landfilling) by reducing the need for "conventional" waste disposal and • lower greenhouse gas emissions as compared to plastic production. • Recycling is a key component of modern waste reduction and is the third component of the "Reduce, Reuse and Recycle" waste hierarchy. Waste Disposal
- 37. • Incepta , United States EPA, Pollution Prevention Fact Sheet, Washington, DC, March 1991. • Keoleian , G., and D. Menerey , "Sustainable Development by Design: Review of Life Cycle Design and Related Approaches," Air & Waste, 44, May 1994. • Theodore, L. Personal notes. • Dupont, R., L. Theodore, and K. Ganesan, Pollution Prevention: The Waste Management Approach for the 21st Century, Lewis Publishers, 2000. • World Wildlife Fund, Getting at the Source, 1991, p. 7. • United States EPA, 1987 National Biennial RCRA Hazardous Waste Report-Executive Summary, Washington, DC, GPO, 1991, p. 10.ASTM, Philadelphia, PA. • Theodore, L., and R. Allen, Pollution Prevention: An ETS Theodore Tutorial, Roanoke, VA, ETS International, Inc., 1993. • United States EPA, The EPA Manual for Waste Minimization Opportunity Assessments, Cincinnati, OH, August 1988. • Santoleri, J., J. Reynolds, and L. Theodore, Introduction to Hazardous Waste Incineration, 2d ed., Wiley, 2000. • http://www.navanapharma.com/ • Khan Associates, (2006), Environmental Management Plan of Navana Pharmaceuticals Ltd., Environmental Consulting Farm, Dhaka, Bangladesh. • Medical Waste Rules, 2008 • Khan Associates, (2006), Effluent Treatment Plant Design of Navana Pharmaceuticals Ltd., Environmental Consulting Farm, Dhaka, Bangladesh. References
- 38. THANK YOU