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Hazards of Oily Waste & its Remediation 
1 
Lecture 
at 
Department of continuing education IIT, Roorkee 
27th January, 2010 
G.S. Dang 
gurbax49@gmail.com
2 
Presentation Outline 
Oily Wastes / Hazardous Wastes 
Sludge Generation/ Environmental Regulations 
Sludge Management / Bioremediation 
Other disposal ways 
Conclusion
3 
Oily Wastes 
Sources: 
 Crude oil spills 
 Oily sludge generated in crude oil tanks in oil fields 
and in refineries 
 Oil contaminated soil / drill cuttings 
 Oil sludge generated in petroleum product tanks in 
refineries / marketing terminals 
 Sludge generated in effluent treatment plants (ETPs) 
in refineries / oil installations
4 
Oily Sludge- Constituents 
 It is a mixture of heavy hydrocarbons like 
asphaltenes and waxes together with sand, clays, 
water and other solid substances like rust and heavy 
metals 
 The sludge is an environment hazard & hazardous 
waste rules apply on it
5 
Hazardous Waste 
Definition (As defined in HW Rules 2008) 
Any waste which by reason of any of its physical, 
chemical, reactive, toxic, flammable, explosive or 
corrosive characteristics causes danger or is likely to 
cause danger to health or environment whether alone or 
when in contact with other wastes or substances is termed 
Hazardous 
and shall include Wastes listed in Schedule–1 (list of 
processes generating waste), Schedule – 2 (concentration 
limits of wastes) of HW Rules
6 
Sludge Generation in Refineries / 
Oil Installations 
 Oily Sludge - Generated from cleaning of the crude 
oil and heavy product storage tanks and also from 
ETP basins 
 Chemical Sludge – Generated in ETP during 
chemical treatment of effluents. (eliminated with 
commissioning of biological treatment plant, BTP) 
 Bio Sludge – Generated from clarifier in BTP during 
biological treatment of effluents 
Sludge is extremely difficult to remove from tanks & 
poses very difficult disposal problems
7 
Oily Sludge(s) – Composition 
Typical high volume hazardous waste generated 
by refineries / storage terminals 
Tank Bottoms Sludge contains 
Crude oil / Product Oil 40 to 80% 
Tanks (FO/Diesel) Water 10 to 40% 
Solids 5 to 15% 
Waste Water Treatment Plant Sludge contains 
 ETP Sludge oil 40 to 60% 
 Emergency Basin / Lagoons water 50 to 55% 
Solids 10 to 15% 
Industry average for total refinery solids production is 
around 0.32 Ton (oil + solids) per 1000 bbl of crude 
processed (API study)
Prevailing Environmental Regulations 
Hazardous waste (Management & Handling rules – 2008) 
requires refineries / oil establishments 
 Facility operator to obtain authorization for handling / 
storage / transportation of sludge 
 Authorization is subject to satisfactory steps taken to 
reduce waste generated 
 Occupier is responsible for treatment of hazardous waste 
& disposal of residual waste 
 Storage of raw sludge is temporarily permitted in 
secured landfill for a period at the end of which it is to be 
treated & disposed off as a part of environmentally 
sound management of hazardous waste 
8
9 
Management of Oily Sludge 
Approach followed : 
 Volume reduction 
 Treatment for recovery of oil 
 Disposal of residual sludge / solids without affecting 
environment
Management of Oily Sludge Contd… 
Volume reduction / oil recovery 
In-situ recovery 
 Operation of side entry mixers – dispersing the 
sludge particles in the bulk of the crude oil 
 Sludge dissolving by hot gas oil (70–80oC) circulation 
10 
in the tank
Management of Oily Sludge Contd… 
Ex-situ recovery 
 Sludge is removed to melting pit 
 Melting of oily sludge by heating to 80-90oC using low 
pressure steam, followed by filtering, centrifuging & 
settling 
 For ETP sludge volume reduction and dewatering is 
done through use of thickeners & centrifuges 
 With this treatment solid content of sludge is increased 
from 1-3% by weight to approximately 20% by weight 
11
Contd… 
 The recovered oil is pumped to slop tanks for 
reprocessing with crude oil. Water phase is sent to 
effluent treatment plant (ETP) 
The residual sludge is disposed off / stored in 
specially constructed pits / secured land fill (SLF) 
having polymer lining and leachate collection 
system 
12 
Management of Oily Sludge
13 
Limitations of Existing Practices 
 Recovery of oil is limited. Residual sludge in melting pit 
contains oil upto 30 to 35 %wt 
 Substantial quantity sludge is to be removed manually 
(messy operation) 
 Leads to pollution due to VOC emissions 
 Manual operation is not only unhealthy / unsafe but leads 
to outage of tanks for very long period (8 to 15 months) 
 Residual sludge is problem for eco-friendly disposal 
 Accumulation / storage of sludge in lined pits (secured 
landfill is not solution on long term basis)
Sludge Management – Bioremediation 
14 
Method 
Residual sludge disposal 
 Bioremediation of residual sludge is well reorganized / 
adopted by refineries and oil producing companies as 
the way to dispose it in environment friendly way
Bioremediation of Residual Oily Sludge 
 Bioremediation is a process that employs 
microorganisms capable of degrading toxic 
contaminants present in hazardous wastes like oily 
sludge etc 
 Naturally occurring microorganisms transform 
harmful substances containing hydrocarbons to 
carbon dioxide and water 
 Safe disposal of sludge without affecting the quality 
of soil and ground water 
15
16 
Bioremediation Methodology 
 Oily sludge is spread over the soil of the earmarked site 
and tilling is carried out 
 Bacterial consortium (oil zapper / oilivorous’S’) is applied 
along with nutrient at the farmed out site 
 The area is tilled every fortnight in 12-16 weeks, all the oil 
gets decomposed to carbon dioxide and water 
 Soil & sludge samples are analyzed every quarter for 
parameters including heavy metal content. No built up of 
concentration of heavy metals (Zn, Mn, Cr, Cu, Ni, Pb, Co, 
As, Cd, Se) in the soil 
 Around 16 weeks of initial application the cycle is 
complete and fresh cycle can be started. No adverse 
impact on quality of ground water
17 
Phytoremediation 
Bioremediation has been broadly successful with 
petroleum based constituents 
Microbial digestion however has met limited success for 
widespread residual organic and metal pollutants 
To remove trace concentration of heavy metals from soil 
and water phytoremediation using certain plants is fast 
emerging 
Type of phytoremediation techniques include 
phytoextraction, phytotransformation, phytostabilization, 
phytodegradation and rizofiltration 
Phytoremediation is well suited for use at very large field 
sites where other methods of remediation are not cost 
effective or practicable
18 
Advantages of Bioremediation 
A way to safe disposal of oily sludge in petroleum 
industry (conventional methods expensive and 
cumbersome) 
Bioremediation produces harmless products like carbon 
dioxide, water and cell biomass 
Technology well accepted in industry 
Commercially used for large quantities of sludge 
(>20,000 MT) 
Cost effective vis-à-vis available technologies
Disadvantages of Bioremediation 
A Bioremediation is limited to those compounds that are 
biodegradable. Not all compounds are susceptible to 
rapid and complete degradation 
Bioremediation often takes longer than other treatment 
options, such an excavation and removal of soil or 
incineration 
Regulatory uncertainty remains regarding acceptable 
performance criteria for bioremediation. There is no 
accepted definition of “clean”, evaluating performance of 
bioremediation is difficult, and there are no acceptable 
endpoints for bioremediation treatments 
19
Other disposal ways 
for 
hazardous wastes
Incineration 
• Incineration is applied to certain wastes that 
cannot be recycled, reused or safely deposited in 
a landfill. 
• Incineration is high temperature, thermal 
oxidation process in which hazardous wastes are 
converted, in presence of oxygen in the air, into 
gases and incombustible solid residue. Gases are 
vented into atmosphere through Gas cleaning 
system and solid residue go to landfill
Incineration 
Applicability of incineration of hazardous 
waste depends on certain considerations: 
• The waste is biologically hazardous 
• It is resistant to biodegradation and persistent 
• It is volatile and therefore easily dispersed 
• It cannot be safely disposed into landfill even after 
stabilization 
• Volume reduction of waste is necessary
Incinerable wastes 
Typical wastes that would need to be 
incinerated by the operator of TSDF 
(waste treatment facility ) may 
include 
- solvent wastes (spent solvents) 
- waste oils, oil emulsions 
- oil mixtures / Refinery waste 
- Others with calorific value > 2500 
Kcal/kg
Guidelines for Incineration 
Incineration aims - destroying the toxicity of wastes and 
get products of combustion that are harmless. The 3 Ts 
of combustion are: 
• Temperature 
• Time 
• Turbulence 
Availability of oxygen is additional parameter which 
forms an integral part of the incineration system.
Guidelines for Incineration 
When waste is burnt at the higher temperature 
destruction would be complete and formulation 
of un-burnt waste, formation of organic by-products 
etc would be eliminated. The longer the 
waste is held at high temperature, the greater will 
be the degree of destruction and the less 
likelihood of formation Products of Incomplete 
Combustion (PICs)
Guidelines for Incineration 
Temperatures of 900-1100 C for hydrocarbon wastes 
and 1100-1200 C for certain waste like PCBs, waste 
Oil residues etc. For other halogenated organics case 
to case tackling may be needed. 
Minimum gas phase residence time of 2 seconds has 
to be maintained 
Combustion air – 100% excess of stochiometric 
requirements 
Turbulence is achieved through good incinerator 
design
28 
Conclusion 
Oily wastes generated in refineries / oil installations are 
hazardous as per HW rules 2008 
Management of oily wastes include recovery of valuable 
oil and separating the hazardous constituents 
Hazardous constituents need to be handled / disposed 
off in a way that the environment pollution is minimum 
Bioremediation is one such way to convert the 
hazardous constituents into harmless products to a 
greater extent 
Research is still on to make the bioremediation process 
as clean as possible 
Bioremediation/ Phytoremediation techniques are 
improving as greater knowledge & experience are gained
Tel: 0135-2654989 
09997168805 
E-mail : gurbax49@gmail.com 
29 
C O N T A C T S
Melting Pit
PVC LINED PIT FOR OILY SLUDGE 
STORAGE
TILLING OPERATION DURING BIOREMEDIATION
SAMPLE BEFORE AND AFTER BIOREMEDITATION 
oily sludgey 
soil sample after 
bioremediation
PHYTO EXTRACTION

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Harards of oily waste & its management

  • 1. Hazards of Oily Waste & its Remediation 1 Lecture at Department of continuing education IIT, Roorkee 27th January, 2010 G.S. Dang gurbax49@gmail.com
  • 2. 2 Presentation Outline Oily Wastes / Hazardous Wastes Sludge Generation/ Environmental Regulations Sludge Management / Bioremediation Other disposal ways Conclusion
  • 3. 3 Oily Wastes Sources:  Crude oil spills  Oily sludge generated in crude oil tanks in oil fields and in refineries  Oil contaminated soil / drill cuttings  Oil sludge generated in petroleum product tanks in refineries / marketing terminals  Sludge generated in effluent treatment plants (ETPs) in refineries / oil installations
  • 4. 4 Oily Sludge- Constituents  It is a mixture of heavy hydrocarbons like asphaltenes and waxes together with sand, clays, water and other solid substances like rust and heavy metals  The sludge is an environment hazard & hazardous waste rules apply on it
  • 5. 5 Hazardous Waste Definition (As defined in HW Rules 2008) Any waste which by reason of any of its physical, chemical, reactive, toxic, flammable, explosive or corrosive characteristics causes danger or is likely to cause danger to health or environment whether alone or when in contact with other wastes or substances is termed Hazardous and shall include Wastes listed in Schedule–1 (list of processes generating waste), Schedule – 2 (concentration limits of wastes) of HW Rules
  • 6. 6 Sludge Generation in Refineries / Oil Installations  Oily Sludge - Generated from cleaning of the crude oil and heavy product storage tanks and also from ETP basins  Chemical Sludge – Generated in ETP during chemical treatment of effluents. (eliminated with commissioning of biological treatment plant, BTP)  Bio Sludge – Generated from clarifier in BTP during biological treatment of effluents Sludge is extremely difficult to remove from tanks & poses very difficult disposal problems
  • 7. 7 Oily Sludge(s) – Composition Typical high volume hazardous waste generated by refineries / storage terminals Tank Bottoms Sludge contains Crude oil / Product Oil 40 to 80% Tanks (FO/Diesel) Water 10 to 40% Solids 5 to 15% Waste Water Treatment Plant Sludge contains  ETP Sludge oil 40 to 60%  Emergency Basin / Lagoons water 50 to 55% Solids 10 to 15% Industry average for total refinery solids production is around 0.32 Ton (oil + solids) per 1000 bbl of crude processed (API study)
  • 8. Prevailing Environmental Regulations Hazardous waste (Management & Handling rules – 2008) requires refineries / oil establishments  Facility operator to obtain authorization for handling / storage / transportation of sludge  Authorization is subject to satisfactory steps taken to reduce waste generated  Occupier is responsible for treatment of hazardous waste & disposal of residual waste  Storage of raw sludge is temporarily permitted in secured landfill for a period at the end of which it is to be treated & disposed off as a part of environmentally sound management of hazardous waste 8
  • 9. 9 Management of Oily Sludge Approach followed :  Volume reduction  Treatment for recovery of oil  Disposal of residual sludge / solids without affecting environment
  • 10. Management of Oily Sludge Contd… Volume reduction / oil recovery In-situ recovery  Operation of side entry mixers – dispersing the sludge particles in the bulk of the crude oil  Sludge dissolving by hot gas oil (70–80oC) circulation 10 in the tank
  • 11. Management of Oily Sludge Contd… Ex-situ recovery  Sludge is removed to melting pit  Melting of oily sludge by heating to 80-90oC using low pressure steam, followed by filtering, centrifuging & settling  For ETP sludge volume reduction and dewatering is done through use of thickeners & centrifuges  With this treatment solid content of sludge is increased from 1-3% by weight to approximately 20% by weight 11
  • 12. Contd…  The recovered oil is pumped to slop tanks for reprocessing with crude oil. Water phase is sent to effluent treatment plant (ETP) The residual sludge is disposed off / stored in specially constructed pits / secured land fill (SLF) having polymer lining and leachate collection system 12 Management of Oily Sludge
  • 13. 13 Limitations of Existing Practices  Recovery of oil is limited. Residual sludge in melting pit contains oil upto 30 to 35 %wt  Substantial quantity sludge is to be removed manually (messy operation)  Leads to pollution due to VOC emissions  Manual operation is not only unhealthy / unsafe but leads to outage of tanks for very long period (8 to 15 months)  Residual sludge is problem for eco-friendly disposal  Accumulation / storage of sludge in lined pits (secured landfill is not solution on long term basis)
  • 14. Sludge Management – Bioremediation 14 Method Residual sludge disposal  Bioremediation of residual sludge is well reorganized / adopted by refineries and oil producing companies as the way to dispose it in environment friendly way
  • 15. Bioremediation of Residual Oily Sludge  Bioremediation is a process that employs microorganisms capable of degrading toxic contaminants present in hazardous wastes like oily sludge etc  Naturally occurring microorganisms transform harmful substances containing hydrocarbons to carbon dioxide and water  Safe disposal of sludge without affecting the quality of soil and ground water 15
  • 16. 16 Bioremediation Methodology  Oily sludge is spread over the soil of the earmarked site and tilling is carried out  Bacterial consortium (oil zapper / oilivorous’S’) is applied along with nutrient at the farmed out site  The area is tilled every fortnight in 12-16 weeks, all the oil gets decomposed to carbon dioxide and water  Soil & sludge samples are analyzed every quarter for parameters including heavy metal content. No built up of concentration of heavy metals (Zn, Mn, Cr, Cu, Ni, Pb, Co, As, Cd, Se) in the soil  Around 16 weeks of initial application the cycle is complete and fresh cycle can be started. No adverse impact on quality of ground water
  • 17. 17 Phytoremediation Bioremediation has been broadly successful with petroleum based constituents Microbial digestion however has met limited success for widespread residual organic and metal pollutants To remove trace concentration of heavy metals from soil and water phytoremediation using certain plants is fast emerging Type of phytoremediation techniques include phytoextraction, phytotransformation, phytostabilization, phytodegradation and rizofiltration Phytoremediation is well suited for use at very large field sites where other methods of remediation are not cost effective or practicable
  • 18. 18 Advantages of Bioremediation A way to safe disposal of oily sludge in petroleum industry (conventional methods expensive and cumbersome) Bioremediation produces harmless products like carbon dioxide, water and cell biomass Technology well accepted in industry Commercially used for large quantities of sludge (>20,000 MT) Cost effective vis-à-vis available technologies
  • 19. Disadvantages of Bioremediation A Bioremediation is limited to those compounds that are biodegradable. Not all compounds are susceptible to rapid and complete degradation Bioremediation often takes longer than other treatment options, such an excavation and removal of soil or incineration Regulatory uncertainty remains regarding acceptable performance criteria for bioremediation. There is no accepted definition of “clean”, evaluating performance of bioremediation is difficult, and there are no acceptable endpoints for bioremediation treatments 19
  • 20. Other disposal ways for hazardous wastes
  • 21. Incineration • Incineration is applied to certain wastes that cannot be recycled, reused or safely deposited in a landfill. • Incineration is high temperature, thermal oxidation process in which hazardous wastes are converted, in presence of oxygen in the air, into gases and incombustible solid residue. Gases are vented into atmosphere through Gas cleaning system and solid residue go to landfill
  • 22. Incineration Applicability of incineration of hazardous waste depends on certain considerations: • The waste is biologically hazardous • It is resistant to biodegradation and persistent • It is volatile and therefore easily dispersed • It cannot be safely disposed into landfill even after stabilization • Volume reduction of waste is necessary
  • 23. Incinerable wastes Typical wastes that would need to be incinerated by the operator of TSDF (waste treatment facility ) may include - solvent wastes (spent solvents) - waste oils, oil emulsions - oil mixtures / Refinery waste - Others with calorific value > 2500 Kcal/kg
  • 24.
  • 25. Guidelines for Incineration Incineration aims - destroying the toxicity of wastes and get products of combustion that are harmless. The 3 Ts of combustion are: • Temperature • Time • Turbulence Availability of oxygen is additional parameter which forms an integral part of the incineration system.
  • 26. Guidelines for Incineration When waste is burnt at the higher temperature destruction would be complete and formulation of un-burnt waste, formation of organic by-products etc would be eliminated. The longer the waste is held at high temperature, the greater will be the degree of destruction and the less likelihood of formation Products of Incomplete Combustion (PICs)
  • 27. Guidelines for Incineration Temperatures of 900-1100 C for hydrocarbon wastes and 1100-1200 C for certain waste like PCBs, waste Oil residues etc. For other halogenated organics case to case tackling may be needed. Minimum gas phase residence time of 2 seconds has to be maintained Combustion air – 100% excess of stochiometric requirements Turbulence is achieved through good incinerator design
  • 28. 28 Conclusion Oily wastes generated in refineries / oil installations are hazardous as per HW rules 2008 Management of oily wastes include recovery of valuable oil and separating the hazardous constituents Hazardous constituents need to be handled / disposed off in a way that the environment pollution is minimum Bioremediation is one such way to convert the hazardous constituents into harmless products to a greater extent Research is still on to make the bioremediation process as clean as possible Bioremediation/ Phytoremediation techniques are improving as greater knowledge & experience are gained
  • 29. Tel: 0135-2654989 09997168805 E-mail : gurbax49@gmail.com 29 C O N T A C T S
  • 31. PVC LINED PIT FOR OILY SLUDGE STORAGE
  • 32. TILLING OPERATION DURING BIOREMEDIATION
  • 33. SAMPLE BEFORE AND AFTER BIOREMEDITATION oily sludgey soil sample after bioremediation