IOCL refinery, Panipat

Sour water Spent caustic

150C 200C 400C

Crude oil storage tank

Desalter

Desalter Effluent

Tank bottom draws (Marine Fuel Oil)

Schematic flowchart: Process & Process waste-streams

Unit operations/ processes Crude Storage Tanks to store the raw material crude oil Desalting to extract corrosive, catalystprohibitive and equipmentfouling salts and compounds Distillation to separate crude oil into groups of hydrocarbon compounds of different boilingpoint ranges Catalytic cracking to break down (decompose) the heavy hydrocarbons (HC) into smaller desired HC products Solvent Extraction for extraction of acid components in intermediate streams

Water use No addition of water

Waste Water Water and sediments that are picked up when the oil is extracted from the wells High temperature, high salt, suspended solids, phenols, H2S Oily sour water (condensed steam containing H2S, NH3)

Hot water to extract salts and chemical compounds Steam is used as stripping medium

Diluent to reduce hydrocarbon partial pressure

H2S, NH3, High pH, phenols suspended solids, BOD, COD.

Caustic solution

Spent caustics residual H2S, phenols, organic acids, HCN, CO2

Major contaminants
Parameter Untreated combined effluent (mg/L) 6 10 30 45 C 100 500 300 500 (5 days, 20C) 500 3000 50 120 20 40 50 70 MINAS (mg/L)

pH Temperature Suspended solids BOD Oil and grease Sulphide Phenols Ammonia as N

6.0-8.5 -20.0 15.0 (3 days, 27C) 5.0 0.5 0.35 15.0

Treatment options
Primary Biological Tertiary

Sour water stripper

H2S, NH3 removal from sour water streams Oil / Water/ Solids separators 1. API separators (Gravity separation)

Organics, BOD removal

Suspended growth process ASP SBR

Residual contaminants
TSS, TDS Membrane filtration MF/UF MF/UF + RO MF/UF + NF Ion exchange softening (also for dissolved inorganics) Dissolved COD, PAH Activated carbon COD, metal & their compounds, nonbiodegradables Chemical oxidation

Attached growth process Bio tower

2. DAF or IAF separators

Zero Liquid Discharge (ZLD)

Oil to slop Refinery WW Primary oil / water separation Sludge Secondary oil / water separation Sludge Tertiary Treatment Oil to slop

Equalization

Biological Treatment

Clarification

Refinery Effluent Recycle Water to Refinery Wastewater Reuse Upgrade (R.O)

Permeate

Water Brine Concentration

Water

Crystallizer

R.O Reject Brine

Salt crystals to Disposals

Pollution prevention opportunities

1. Waste minimization Improved housekeeping Establish leak detection and repair program, Refurbish or eliminate underground piping, Remove unnecessary storage tanks from service, Replace old boilers, Segregate process waste streams

Equipment redesign
Process control/ modification

Modernization of Fired Heaters, Sonic Soot Blowers instead of conventional soot blowers
Control of surfactants in wastewater, Minimize solids leaving the desalter, Modernization of Instrumentation and Advanced Control Strategies, Offsite Automation facilities Switch from Naphtha to Regasified Liquid Natural Gas (RLNG) as feed to Reformer in Hydrogen Unit and firing of all the furnaces no pretreatment of naphtha to remove sulphur Recycle and regenerate spent caustics, Minimize cooling tower blow down, Part of the treated effluents to be recycled for greenbelt development, fire water make up, chemical preparation and other peripheral applications in the Refinery Complex. The remaining treated effluents to be reclaimed for refinery process reuse through ZLD scheme

Substitution of less hazardous material

Recovery, Reuse, Recycle

2.
Design of recycling technology to conserve, recover

Raw material

Reduce the generation of tank bottoms, Detailed Hydrocarbon loss study and remedial measures, Electronic themoprobes for accurate tank temperature to minimize hydrocarbon loss Adoption of co-generation principle for generation of steam / power, etc. which includes installation of FCCU Co Boiler, Maximization of crude preheat by optimization of Heat Exchanger Train using Pinch Technology, Effective use of Waste Heat, On-line oxygen analyzers, Mass flow meters on furnaces / boilers to improve furnace efficiency
Minimize cooling tower blow down, Reclamation of city sewage water for refinery use by employing conventional physico-chemical based tertiary treatment process followed by membrane separation of contaminants through reverse osmosis. An additional train of Reverse osmosis membranes to recover R.O. rejects Identify benzene sources and install upstream water treatment, Hydrogen gas recovery from process units green fuel

Energy

Water

By products

3. Waste utilization

Sludge

Mechanical Oil recovery from oily sludge, Processing of Oily sludge to recover oil, Bio-remediation for oily sludge treatment to produce organic fertilizers

References 1. OSHA technical manual - section IV: chapter 2 Petroleum refining process www.osha.gov/dts/osta/otm/otm_iv/otm_iv_2.html 1/ 2. IPIECA Operations Best Practice Series: Petroleum refining water/wastewater use and management, 2010 3. Treatment of Oilfield and Refinery Wastes, Joseph M. Wong and Yung-Tse Hung, Taylor & Francis Group, LLC, 2006

4. EPA Office of Compliance Sector Notebook Project: Profile of the Petroleum Refining Industry, September 1995
5. The Oil and Gas Sector Overview in India 2009, KPMG India Private Ltd. 6. Official website: Chennai Petroleum Corporation Ltd.http://www.cpcl.co.in 7. Official website: Hindustan Petroleum Corporation Ltd. http://www.hindustanpetroleum.com