Oil refinery water overview-

Oil refineries are multioperation systems that are dependent on the kind of oil need to be processed
and the outputs that are being targeted. With the several kinds of processes being performed, crude
products and size, the industry becomes a large consumption of water, as compared to other
industries and consumers.

Although water is needed in many operations in an oil refinery, not every process requires raw or
processed water, and water may be cascaded or reused in many areas. A large portion of the water
is used in oil refinery and may be recycled on a continuous basis. Steam losses, as well as cooling
tower evaporation and drift, contribute to atmospheric losses. A little amount of water can also be
carried away with the products. Certain operations, such as steam generating systems or cooling
water systems, need a continuous supply of water to the process.

Sources of wastewater-

Surface water- Water for the refinery can come from a variety of sources, including rivers and lakes.
It may also come from the sea or other brackish water sources in some cases. Groundwater in
aquifers can provide an additional source of water if the subsurface water is readily accessible.
Characteristics of raw water includes- total suspended solids, total dissolved solids and turbidity.

Purchased water- A refinery's potable water (drinking and sanitary water) is typically obtained from
a local municipality. Potable water may also be obtained from groundwater aquifers or other
alternate sources if they are accessible.

Water in crude- Entrained water from the oil well extraction process or absorption during
transportation is common when crude arrives at a refinery. The water is normally extracted as
bottom sediment and water in storage tanks or in the refinery's desalter (which is part of the crude
unit), is then transferred to wastewater treatment.

Rain- Rain is another supply of water for a refinery. Rain that falls within the refinery's battery
capacity is usually handled before being discharged. Depending on local restrictions, rain that falls in
non-industrial portions of a refinery, such as parking lots, green spaces, or administrative housing,
may be discharged without treatment.

WASTE WATER TREATMENT-

Typical refinery wastewater treatment plants consist of primary and secondary oil/water separation,
followed by biological treatment, and tertiary treatment (if necessary).

Two phases of oil removal are normally required in a refinery wastewater treatment system to
achieve the necessary removal of free oil from the collected wastewater prior to feeding it to a
biological system. An API separator is used first, followed by a dissolved air flotation (DAF) or
induced air flotation (IAF) unit to remove the oil. The wastewater from the secondary oil separation
unit is transported to the equalize system, which is utilised to smooth off flow and concentration
irregularities in the refinery wastewater. The wastewater is then sent to the biological system's
aeration tank and clarifier. The clarifier's effluent is then routed to tertiary treatment before being
discharged.

Primary treatment- A physical process, generally gravity separation, is used to remove the floating
and settleable elements in refinery effluent as the main treatment. The primary treatment stage in a
conventional refinery wastewater treatment system is an oil separator, which separates oil and
particles. After that, a DAF or an IAF unit is employed in a secondary oil separation process.

API Separator- API separators are commonly widely used for the treatment of refinery effluent,
which typically comprises oil and sludge containing oil. Separators work by allowing heavier
materials to flow below lighter liquids due to differences in specific gravity. In a conventional API
separator, wastewater is collected first in a pre-treatment section to remove sludge. A diffusion
barrier slows the flow of wastewater through the separator to the output, allowing the lighter oil
fractions to be skimmed off. Heavier particles are sometimes removed with flights and scrapers. Oil
is normally prevented from leaking into the output portion by using underflow baffle plates. A typical
API separator is shown in Figure

Secondary Separation-

The effluent from the primary oil separation process is transferred to a DAF or IAF unit for additional
oil and fine particles removal. The selection of whether to utilise a DAF or an IAF unit is refinery-
specific, and it must be made based on the influent and desired outlet conditions.

Dissolved air floatation- Coagulation/ flocculation is the initial phase in a DAF system. Negative
electric charges on the surfaces of dispersed particles (oil/solids) stabilise them, forcing them to
resist each other. They do not settle because this stops these charged particles from interacting and
forming bigger masses known as flocs.

Chemical coagulation and flocculation are necessary to aid in the removal of colloidal particles from
solution. These treatments, which are normally carried out in order, are a mix of physical and
chemical procedures. To induce the aggregation of suspended materials into particles big enough to
settle or be removed, chemicals are combined with wastewater.

SECONDARY TREATMENT-

In the oil refining industry, biological treatment is the most commonly applied wastewater
treatment process for removing dissolved organic pollutants.

Biological therapy may be divided into two categories: suspended growth processes and attached
growth processes.

Suspended growth process-

Suspended growth techniques are biological treatment methods in which microorganisms are fully
mixed with organics in a liquid and kept suspended in the liquid. Microorganisms feed on organic
compounds and cluster together to generate active biomass. The 'activated sludge method' is the
most often employed suspended growth procedure in the treatment of refinery effluent.

 Activated sludge process- Of all the biological systems known, the activated sludge process is
the most effective. It is widely utilised in refineries across the world and provides a
dependable biological treatment approach.
In an activated sludge process, wastewater is fed into an aeration tank, where
microorganisms come into contact with the wastewater's organic pollutants. To keep the
sludge aerobic and the solids suspended, air is continually fed into the system. The biomass
in the aeration basin/tank is known as 'mixed liquor suspended solids,' and the mixture of
wastewater and sludge is referred to as 'mixed liquor' (MLSS). 'Mixed liquid volatile
suspended solids' is a term used to describe the organic element of biomass (MLVSS). The
MLSS in a typical refinery wastewater treatment system are made up of 70–90% active
MLVSS and 10–30% inert materials.
 Sequencing batch reactor - A sequencing batch reactor (SBR) is a semi-batch biological
treatment option that combines aeration, sedimentation, and clarifying in one reactor. Both
SBR and activated sludge systems use the same aeration and sedimentation unit procedures.
Unit operations in activated sludge systems take occur in multiple basins, whereas SBR
activities take place in a single basin in a sequential manner.

Attached growth process-

Instead of being suspended in the liquid as in suspended growth processes, microorganisms are
connected to an inert packing material in attached growth processes. Rocks, gravel, plastic material,
and numerous synthetic materials can all be employed as packing in the attached growing methods.
The wastewater interacts with the microorganisms adhering to the medium, resulting in the
production of additional biomass and CO2. The biomass coating on the medium continues to
develop and eventually washes away when it reaches a specific thickness.

 Trickling filter- In the trickling filter, a slime layer (microorganisms) forms on the packing.
Microorganisms biodegrade the organics in the wastewater as it flows through the trickling
filter bed, allowing them to be removed from the liquid running over the packing. A final
 clarifier, placed directly downstream of the filter, removes microbial growths that slough off
from the filter medium on a regular basis.
 Rotating biological contactor - The rotating biological contactor (RBC) is made up of closely
spaced plastic discs that are attached on a horizontal shaft. Polystyrene or polyvinyl chloride
are commonly used as disc materials. These plastic discs are submerged in wastewater and
revolve continually thanks to an air-driven motor on the horizontal shaft. Microorganisms
attach to the plastic surface of the discs, forming a coating of biological material (slime).
Excess sludge is sloughed off the discs over time. The attached microbes react with the
pollutants in the wastewater as the discs rotate, converting them to biomass and CO2.

TERTIARY TRAETMENT-

If the refinery has to fulfil desired limits for pollutants including total suspended solids (TSS),
chemical oxygen demand (COD), dissolved and suspended metals, and trace organics like
polyaromatic hydrocarbons, tertiary treatment should be explored (PAHs).

 Sand filtration- Depending on the working parameters of the clarifier, the effluent from
the biological treatment system generally comprises 25 to 80 mg/l of suspended
particles. Many refineries are required to satisfy standards as low as 15 mg/l on a regular
basis. In these cases, sand filters can be used to filter the clarifier's effluent.
 Activated carbon- Carbon adsorption can be used to remove dissolved organic
components from refinery effluent. Activated carbon is commonly used as an effluent
'polishing' step (removal of residual organics) for wastewater that has gone through a
biological treatment system. This is because the carbon footprint of treating refinery
effluent would be significantly large.
 Chemical oxidation- In a refinery, chemical oxidation is commonly utilized to minimize
residual COD, non-biodegradable chemicals, and trace organic molecules. In a refinery
wastewater treatment scheme, a chemical oxidation system is uncommon. In certain
situations, chemical oxidation can be increased by using UV light as a catalyst, although
this must be determined on a case-by-case basis.

SLUDGE MANAGEMENT

REUSE, RECYCLE

CASE STUDY(MAY BE HPCL)

Hindustan Petroleum Corporation Limited (HPCL)

HPCL is a subsidiary of Oil and Natural Gas Corporation, which is owned by the Ministry of Petroleum
and Natural Gas of the Government of India. It has a 25% market share among public sector
undertakings (PSUs) in India, as well as a powerful marketing infrastructure. HPCL runs two main
refineries, one in Mumbai (West Coast) with a capacity of 7.5 million tonnes per year and the other
at Visakhapatnam (East Coast) with a capacity of 8.3 million tonnes per year, both of which
produce a wide range of petroleum fuels and specialities. Products by HPCL includes- Petrol, Diesel,
Lubricants, Liquified petroleum gas, Emulsions.
Efficient Process for Spent-caustic Wastewater Treatment-

Scrubbing solutions containing sodium hydroxide (caustic) are widely utilized in petrochemical and
oil refineries to remove acid components from refined product streams such as hydrogen sulphide,
cresylic acids, mercaptan, and naphthenic acids. Handling and disposing of used caustic can be
difficult due to the toxic, odorous, and/or corrosive components. Other features of spent caustic
streams that can cause problems with traditional biological processes include strong odours, pH
fluctuations, foaming, and poor settling of biological materials. Because certain waste caustic
pollutants are not biodegradable, meeting effluent regulations may be challenging.

Wet air oxidation (WAO) and direct acid neutralisation (DAN) are the two most used procedures for
handling waste caustic solutions. However, due to excessive acid consumption and considerable
caustic waste to effluent, these approaches are ineffective. The wasted caustic is refined and harmful
elements are eliminated in this experimental process, and two important products, NaOH and
Na2CO3, are created with high purity through an efficient procedure. Advanced oxidation will oxidise
all reduced sulphur compounds and phenols, eliminate the spent caustic's foaming nature, and
reduce the majority of COD, resulting in biodegradable wastewater. AO is suitable for refinery waste
caustics that contain naphthenic components and are used to treat heavy goods.