8/7/2019 raju final

1/24

A

SEMINAR REPORT

ON

Sources and characteristics ofPollutants in

Petroleum and petrochemical industries

Submitted By

j.raju 07H61A0818

Departmentof Chemical Engineering

COLLEGE OF ENGINEERINGHYDERABAD

2007-2011

\1

8/7/2019 raju final

2/24

CERTIFICATE

This is certify that the report entitled Sources and characteristics of

Pollutants in Petroleum and petrochemical industries is beingsubmitted by J.RAJU ( 07H61A0818) .In partial fulfillment for the

award of the B.Tech (chemical) from C.V.S.R COLLEGE OF

ENGINEERING affiliated to JNTU, HYDERABAD is a record of

bonified work carried out under our guidance and supervision duringthe academic year 2010-2011.

(Dr. M. Bhagvanth Rao)

Professor& Director

(HOD Chemical Engineering Dept)

CONTENTS

\2

8/7/2019 raju final

3/24

ABSTRACT

DEFINITION

CLASSIFICATION

EXPLANATION

SOURCES AND CHARACTERISTICS

EFFECTS ON ENVIRONMENT

CONTROL TECHNIQUES

CONCLISION

REFERENCES

ABSTRACT:-

\3

8/7/2019 raju final

4/24

The source and characteristic of pollutants in petrolium and

petro chemical indusssssssss

Classification of pollutants:-

\4

8/7/2019 raju final

5/24

Pollutants

Primary pollutants secondary pollutants

1. Primary pollutants:

These pollutants emitted directly from identifiable sources.

Primary emissions include particulate matter, sulphur compounds, organic

compounds, nitrogen compounds, carbon compounds, halogen compounds, radio

active compounds etc.

2. Secondary pollutants:

These pollutants produce in the air by interaction among to or from primary

pollutants or by reaction with normal atmosphere constituents.

These pollutants are formed by interaction between various primary pollutants

and/or normal constituents of air.

Examples of these pollutants are formation of sulphuric acid mist, smoke etc.

POLLUTANTS FROM PETROLEUM AND PETROCHEMICAL

INDUSTRIES:

\5

8/7/2019 raju final

6/24

1. Air pollutants:

Major air pollutants that may be emitted from refining operations are

1. Sulfur compounds

2. Hydrocarbons

3. Nitrogen oxides

4. Particulates including smoke

5. Carbon monoxide

Other emissions

1. Aldehydes

2. Ammonia

3. Odors

Petroleum refineries differ in the type of processing schemes employed, type of

units used in a given processing scheme, the type of crude or crude processed,

varieties of end products, location, source of power, utilities requirements and

operating and housekeeping practices.

All these factors have a bearing in varying degrees on the quantities of emissions

from each refinery. Consequently it is desirable to undertake individual refinery

measurements or calculations to estimate factors for this purpose.

A survey of gaseous emissions from petroleum refineries is given in table below

POLLUTANTS EMISSION

\6

8/7/2019 raju final

7/24

S.NO TON/DYY

1

Carbon monoxide 13

2

Hydrocarbons 7

3

Aldehydes, organic acids 1

4

Sulphur dioxide 5

5

Nitrogen oxides 4

1. Sulphur compound:

Sulphur dioxide constitutes the maximum proportion of sulphur compound emitted

from refineries.

The main sources of sulphur dioxide are fuel combustion which are emitted from

combustion operations, such as fires heaters, boilers and catalytic cracking

regenerators and from sulphur dioxide extraction plants.

Any organic sulphur contained in a fuel is oxidized to sulphur dioxide or sulphur

trioxide during combustion. Normally about 97% of the fuel sulphur to sulphur

trioxide during combustion. Eventually however considerably more of the sulphur

dioxide is oxidized to sulphur trioxide in the ambient air, ultimately forming sulphate

particulates.

The amount of sulphur dioxide emission depends upon the type and amount of fuel

burnt and its sulphur content.

Emissions of oxides of sulphur are expressed in terms of sulphur dioxide knowing the

quantity of fuel used based either on flow meter reaching or actual tank gauges, and

the sulphur content of the fuel from actual laboratory analysis, the emissions of

sulphur dioxide may be easily calculated. Actual monitoring of stack gases on such

cases may not n[be necessary.

\7

8/7/2019 raju final

8/24

Refinery flares incinerators and decoking operations are other minor sources.

Other sulphur components emitted from refineries hydrogen sulphide, sulphur trioxide

and mercaptants from treatment processes. However, these emissions are in from

evaporation of leaks and vent losses from storage facilities.

2. Hydrocarbons:

The emissions of hydrocarbons result mainly from evaporation of light oil during

storage and handling of crude and petroleum products and from leaks.

Sources of hydrocarbon emission include loading facilities, sampling, sampling,

storage tanks, and waste water separators. The extent of these emissions depends upon

design maintenance and operating practice.

These emissions cannot be directly measured except in the case of unburnt

hydrocarbons released during combustion operations. These may be measured by

direct stack monitoring.

The major sources of hydrocarbon emission however, are evaporation losses from

storage tanks and from oil separators. These losses can only be estimated by

empherical formulae based on extensive testing and experience.

3. Oxides of nitrogen:

Combustion of fuel in fired heaters and boilers and internal combustion engines used

to drive compressors and electric generators are the main sources of nitrogen oxides

are also released from catalytic cracking regenerators and from co boilers.

Combustion of fossil fuels produces nitrogen oxides partly from the combination of

atmospheric nitrogen with excess oxygen in the furnace atmosphere, and partly from

combination of nitrogen oxides is mainly dependent on the flame temperature. The

residence time at this temperature and the excess air present in the flame.

4. Particulates:

\8

8/7/2019 raju final

9/24

The major sources of emission of particulates in the petroleum refineries are catalytic

cracking regenerators.

The minor sources include internal combustion engines used to drive compressors and

electrical generators and incinerators.

Incomplete combustion in furnaces and boilers also generates carbon monoxide

emissions.

The only significant source of carbon monoxide is the catalytic cracking regenerator.

When co boiler is not employed. No emissions of carbon monoxide are released.

When co boilers does not exist the emissions can be accurately calculated based on

stock gas analysis for carbon monoxide content and the quantity of air used for

regeneration, which is measured and controlled.

5. Carbon monoxide:

The only significant source of carbon monoxide in refineries is the catalytic cracking

regenerators. This, however is eliminated in units a CO boiler.

The minor sources include internal combustion engines used to drive compressors and

electric generators and incinerators. Incomplete combustion in furnaces and boiler and

also in generates CO emissions.

The only significant source of CO is the catalytic cracking regenerator when CO

boiler is not employed. No emissions of CO or released when CO boilers are used.

Where CO boilers do not exist the emissions can be accurately calculated based on

stock gas analysis for CO content and the quantity of air used for regeneration which

is measured and controlled.

11. Effects of Air pollutants on the environment:

1. Reduction in visibility

\9

8/7/2019 raju final

10/24

2. Damage to the material

3. Damage to vegetarian

4. Physiological effects on man and animals

5. Physiological effects

3. AIR POLLUTANTS CONTROL TECHNIQUES AND OPTIONS:

The control of air pollution is an expensive and complex problem because the

character and quantity of refinery atmospheric emissions vary greatly from

refinery to refinery.

Refinery air pollution control techniques exist which should permit refineries to

operate in any community without constituting a serious air pollution problem. A

realistic control strategy, size of the installation, cost benefits, commercial and

possibility of creating other disposal problems.

The majority of refinery emissions occur during combustion in providing power

and heat for processing operators. These include combustion of fuel in boilers for

steam generation combustion of fuel in fired heaters and combustion of carbon

during regeneration of cracking catalysts.

1. CONTROL OF EMISSIONS FROM REFINERY PROCESS GASES:

Minimize sox emission either through desulfurization of fuels to the extent feasible

or by directing the use of high sulfur fuels to units equipped with so x emission

controls.

Nearly all refineries process generates gases which generally contain hydrogen

sulphide or other low molecular weight sulphur compounds. These gases are

normally used as fuel in fired heaters and reboilers.

The most common procedure for removal of hydrogen sulphide and light

mercaptants involves scrubbing the gases with an solution. Solvent such as

aqueous amine solution. The amine solution extracts the hydrogen sulphide and id

then regenerated by stripping hydrogen sulphide with heat and/or steam. The

regenerated solution is reused for further absorption. The hydrogen sulphide

\10

8/7/2019 raju final

11/24

recovered from this process can be converted to either sulphuric acid or elemental

sulphur.

Prevention and control of pollution in petroleum:

Petroleum refineries are complex plants, and the combination and

sequence of processes is usually very specific to the characteristics of

the raw materials (crude oil) and the products. Specific pollution

prevention or source reduction measures in these areas should be

designed into the plant and targeted by management of operating

plants.

Reduction of air emissions:

1. Minimize losses from storage tank and product transfer areas by

methods such as vapor recovery systems and double seals.

2. Minimize SOx emissions either through desulfurization of fuels, to

the extent feasible, or by directing the use of high-sulfur fuels to

units equipped with SOx emissions controls.

3. Recover sulfur from tail gases in high-efficiency sulfur units.

4. Recover non silica-based (i.e., metallic) catalysts and reduce

particulate emissions.

5. Use low-NOx burners to reduce nitrogen oxide emissions.

6. Avoid and limit fugitive emissions by proper process design and

maintenance.

7. Keep fuel usage to a minimum.

Elimination or Reduction of pollutants:

\11

8/7/2019 raju final

12/24

1. Consider reformate and other octane boosters instead of tetraethyl

lead and other organic lead compounds for octane boosting.

2. Use non-chrome-based inhibitors in cooling water, where

inhibitors are needed.

2. WATER POLLUTANTS:

Water pollution due to discharge of industrial wastes has already become a serious

problem in certain areas of the country. The current practices adopted for the

disposal of industrial wastes in the country include discharge into public sewers,

rivers or sea through creeks and estuaries and on land.

Water is used in petroleum refineries for a variety of purposes. Since water does

not enter into the final product, it can be expected that 80-90% of the water

supplied to the refinery comes out as waste water. The characteristics of waste

water from petroleum refineries in India and their pollutant. It indicates that large

volumes of waste water are being discharged containing a variety of objectionable

and toxic organic and inorganic substances. If these waste water are not treated to

the desired degree, the pollutants reach the water course and bring out a number of

chances in the quality of the receiving water, which ultimately render the water

unsafe for aquatic life and for domestic and industrial use.

\12

8/7/2019 raju final

13/24

\13

8/7/2019 raju final

14/24

]CHARACTERISTICS OF WASTE WATER AND POLLUTANTS/TOIX

CONSTITUENTS:

SI NO Effluents characteristics VALUE Pollution/toxic constituents

1 Flow, l/kg oil 1.5 1. free oil(2000-3000 mg/l)

2 pH 6.8-7.2 2. emulsified oil(80-120

mg/oil)

3 Suspended solids, mg/l 200-400 3.H2S & RSH (10-220)

4 BOD, mg/l 100-300 4. Phenols (12-30 mg/l)

5 COD , mg/l ------ 5. Ammonia andchromium if cooling

water is mixed with

process water.

6 BOD/COD ------

7 BOD load, gm/unit product 0.3

TYPES OF WATER POLLUTION:

1. PHYSICAL POLLUTION

2. CHEMICAL POLLUTION

3. PHYSIOLOGICAL POLLUTION

4. BIOLOGICAL POLLUTION

1. PHYSICAL POLLUTION:

\14

8/7/2019 raju final

15/24

This is due to temperature, turbidity, suspended matter. Color, foam and

froth and radioactivity

Waters with higher temperature are usually encountered from thermal power

stations, cooling systems, etc. A mere rise of temperature by a few degreescentigrade decreases the solubility of oxygen in water and this can affect the

receiving stream in two ways. It will increase the biological activity vis--vis

decrease the dissolved oxygen (DO) content and secondly, it will make the fish

migrate to other areas because of low DO and higher temperature. Because of

this, tolerance limits for temperature are prescribed for waste water for

discharge into inland surfaces waters.

Color in general considered as aesthetic pollutant. Color can be associated with

natural as well as artificial substances. Color can reduce photosynthetic activity.

2. CHEMICAL POLLUTION:

This can be due to inorganic and organic chemicals. Inorganic chemicals

include acids, alkalies, heavy metals, soluble salts or inert insoluble substances.

Inorganic acceleration corrosion of metals destroys cotton textiles, kill aquatic

organisms and burn or irritate the skin of animals and humans. When pH of the

water is below 5, the damage is greater. Both acids and alkalies can be toxic to

all aquatic organisms and thus inhibit self purification in streams.

Waste containing free chlorine, chloramines, ammonia, soluble sulphides and

salts of metals such as arsenic, cadmium, chromium, copper, lead, mercury,

nickel, selenium etc. are also highly toxic. These are toxic to fish and also to

humans.

Some of the metals accumulate in ecosystems and reach man and animals.

Soluble salts commonly found in streams include chlorides, sulphates and

bicarbonates of sodium, potassium, calcium, magnesium, iron and manganese.

Sources of oil pollution are from waste waters discharged from ships and oil

tankers, oil refineries, industrial plants handling oil and grease, lubrication of

machinery, metal reduction works, petroleum production spills and wastes.

3. PHYSIOLOGICAL POLLUTION:

\15

8/7/2019 raju final

16/24

Taste and odour constitute physiological pollution. Several industrial wastes

contain chemicals which impart characteristic and unpleasant taste to water.

Salts of iron and manganese, chlorine, hydrogen sulphide, phenols, can be cited

as examples. Water pollution by industrial wastes containing taste-producing

substances may damage the value of fisheries.

4. BIOLOGICAL POLLUTION:

It is a result of discharge of waste water containing pathogenic forms of

bacteria, fungi, algae, viruses, protozoa and halminthic parasites.

This type of pollution is often a secondary result due to contamination by

sewage or industrial wastes. The diseases related to biological pollution are

cholera, typhoid, dysentery, gastroenteritis, and polio-myelitis.

CONTROL OF WATER POLLUTION:

The uses of water can be categorized as drinking, cooling, boiler feed, direct

processing, sanitary and fire protection. The effluent waste originated can be

classified under:

a. Water free from oil

b. Sanitary sewage

c. Process effluents.

The water free from oil includes storm water from oil free catchment areas,

water treatment plant effluent, boiler blown down etc. The process effluents are

basically oily waters originating from different sources, such as drainage from

pump houses, blow down from cooling systems, desalter water, overhead

condensate water from process units, spent caustic etc.

For effective treatment of the effluent water, the streams are segregated throughseparate drainage systems and treated accordingly. The effluent treatment is

usually divided into three categories, i.e., primary, secondary and tertiary

1. PRIMARY TREATMENT METHODS:

\16

8/7/2019 raju final

17/24

This treatment consists of oil removal in two stages by physical methods.

Various physical methods are available and these can be classified as baffling,

floatation, skimming, stripping, stripping and extraction.

The first stage of oil removal is done in small pond or basin where majorportion of oil is removed by using baffling, floatation and skimming methods.

The second stage of oil removal is mainly API(American petrol institute)

separators or other gravity separators, where the remaining oil is removed as a

rule should not be omitted as it lessens the oil load on API or gravity separators

and helps in the efficient removal of oil.

2. SECONDARY TREATMENT METHODS:

These methods can be classified as follows:

a. Chemical method

b. Biological method

The main purpose of chemical method is to remove emulsified oil with addition

of flocculating agents and also to remove suspended solids and toxic substances

and thereby condition of effluents for further treatment by biological method.

Biological treatment aims at the removal of all oxidizable and organic matterfrom the waste water. This method of treating waste water employs the use of:

1. Activated sludge process. Conventional and modified

2. Trickling filters

3. Oxidation ponds

4. Aerated lagoons

The activated sludge process is an aerobic biological treatment process. The

conventional process consists of an aeration tank followed by a sedimentation

\17

8/7/2019 raju final

18/24

tank. In this process high concentrations of newly grown and recycled microbial

biomass are suspended uniformly throughout holding tank to which raw

wastewaters are added.

The tricking filter is a packed media covered with biological slime throughwhich water is percolated.

The treatment of waste water is oxidation ponds provide biological oxidation

and sedimentation similar to that occurring in lakes. Its maintain attraction is

the low cost of construction and operation, but it requires more space and

considerably long detention periods.

The aerated lagoon is smaller, deeper oxidation pond equipped with mechanical

aerators or diffused air units. The addition of oxygen enables the aerated lagoon

to have a higher concentration of microbes than the oxidation pond. The

retention time in aerated lagoons is usually shorter, between 3 and10 day.

3. TERTIARY TREATMENT METHODS:

This treatment has been limited to activated carbon filteration process and

ozonation which are effective in removal of the taste and odour and organics

from biologically treated waste waters. The treated water which satisfy the

relevant tolerance limits are finally disposed by controlled dilution into the

neighbouring stream, river or sea.

SUSPENDED SOLIDS:

Suspended solids causing turbidity tend to reduce light penetration. This may or

may not be beneficial depending upon circumstances and water. For instance

turbidity caused by suspended silt and clay retards algal growth and when this

water is used for drinking.

PH :

\18

8/7/2019 raju final

19/24

The hydrogen ion concentration of a raw-water source for domestic water is

important as it affects taste, corrosivity, efficiency of chlorination, treatment

processes such as coagulation and industrial applications.

TEMPERATURE:

The increase of stream temperature due to mixing of waste waters causes

undesirable stream conditions such as decreased oxygen capacity, increased

oxygen demand, anaerobic zones and purification of sludge deposits. The

toxicity of many substances is intensified as the temperature rises.

BIOCHEMICAL OXYGEN DEMAND:

In itself, BOD is not a pollutant and exercises no direct harm. However, BOD

does exert an indirect effect by depressing the dissolved oxygen content to

levels that are inimical to fish life and other beneficial uses. BOD effect can be

overcome by reaeration, dilution and/ or photosynthetic effect.

OIL AND GREASE:

Oil in inland surface waters may interfere with gas exchange, coat bodies of

birds and fish and exert a direct toxic action on some organisms as a result of

water soluble components. Oil in water bodies used as a source of domestic

water supply has the following deleterious effects.

a. Hazard to the health of consumers.

b. Production of unpleasant tastes and odours

c. Presence of turbidity, films involving aesthetic problems.

d. Increased difficulty of water treatment.

PHENOLIC COMPOUNDS:

\19

8/7/2019 raju final

20/24

In water for domestic use harmful concentrations of phenol are much higher

than taste considerations would allow. The concentration of Phenolic

compounds is limited to 0.001 mg/l in drinking water because of tastes resulting

from the action of chlorine on such waters.

CHEMICAL OXYGEN DEMAND (COD):

The determination of COD provides a measure of the oxygen equivalent of that

portion of the organic matter in a simple that is susceptible to oxidation by

strong chemical oxidant. It is important, rapidly measured parameters for

stream and industrial waste studies and for the control of treatment plants with

certain wastes containing toxic substances. The test may be the only method for

determining the organic load. Where wastes contain only readily available

organic bacterial food and no toxic matter, the results can be used toapproximate the ultimate carbonaceous BOD values.

This method however fails in the absence of a catalyst to include some organic

compounds, such as acetic acid which are biologically available to the stream

organism, while including some biological compounds, such as cellulose, which

are not a part of the immediate biochemical load.

Total dissolved solids (TDS). TDS in irrigation water has direct physical effect

in prevention of water uptake by plants (osmotic effect); hence the need torestrict the TDS in irrigation water. Moreover indirect through changes in soil

structure, permeability and aeration also occurs.

BORON:

Although traces of boron are essential for growth of all plants, more than 0.5

mg/l will be injurious to certain plants, like citrus fruits, plums, apples etc.

crops such as potatoes, tomatoes, wheat etc. can tolerate boron up to 2.0 mg/l.

111. SLUDGE TREATMENT AND DISPOSAL:

\20

8/7/2019 raju final

21/24

Sludge is the suspension of solids in process waters and aqueous wastes.

Sludges produced includes:

1. Crude tank bottoms

2. Slop oil emulsion sludge

3. Cooling tower sludge

4. Lube oil filter cake

5. Heat exchanger bundle cleaning sludge

Sludge is to be prepared and treated for environmentally sound disposal. The

oil content is high. This oil needs to be separated and recirculated. Various

hazardous constituents are needed to be removed ex. Polychlorinatedbiphenyls (PCB).

SLUDGE CHARACTERISTICS:

Sludge must be characterized for pathogenicity, toxicity and various rheological

properties. Sludges need to be tested for pathogenicity. The pathogens organisms

of most concern are some bacteria, viruses, protozoans and parasites, such as

Taenia saginata, potato cyst nematodes and Ascaris. Besides pathogenicity, sludes

need to be tested for toxicity. A range of testes are available for specifictoxicological effects.

SLUDGE CONDITIONING:

Sludge conditioning may be used to increase solids concentration, improve

recovery or reduce thickening time. This can be achieved by chemical addition or

thermal treatment.

CHEMICAL CONDITIONING:

\21

8/7/2019 raju final

22/24

It involves the use of either inorganic or organic chemicals. The most commonly

used inorganic chemicals for conditioning sludges include lime, ferrous and ferric

sulphates, ferric chloride and alum. Organic polyelectrolytes have been used in

sludge conditioning. These fall into three classes: non organic, anionic and

cationic. The chosen polyelectrolyte should have a charge opposite to that on thesludge particles.

THERMAL CONDITIONING:

The primary function of thermal sludge conditioning is to improve dewaterability.

The advantages of this process include reduced solids quantity, low or very low

specific filtration resistance, sterilization and enhanced activated sludge digestion.

The disadvantages include complex equipment arrangements, including high

pressure and temperature vessels, a serious potential for corrosion, relatively highenergy requirements, potentially severe odour problems, and the production of a

sidestream waste.

\22

8/7/2019 raju final

23/24

CONCLUSION:

REFERENCES:

Alberini, Anna and Alan Krupnick (2000). Cost-of-Illness and WTP Estimates of the

Benefits of Improved Air Quality: Evidence from Taiwan,Land Economics 76(1).

\23

8/7/2019 raju final

24/24

Asch, P. and Joseph, J. S. (1978). Some Evidence on the Distribution of Air Quality,

Land Economics, 54, 279-297.

Brainard, J. S., Jones, A.P., Bateman, I. J. and Andrew A. Lovett (2004). Modelling

Environmental Equity: Exposure to Environmental Urban Noise Pollution in

Birmingham, UK, CSERGE, Working Paper EDM 03-04, University of EastAnglia, Norwich (http://www.uea.ac.uk/env/cserge/ pub/wp/

edm/edm_2003_04.pdf)

Brajer, Victor, and Jane V. Hall, (1992). Recent Evidence on the Distribution of Air

Pollution Effects, Contemporary Economic Policy, 10(2): 63-71

Brooks, N. and Rajiv Sethi (1997). The Distribution of Pollution: Community

Characteristics and Exposure to Air Toxics,Journal of Environmental Economicsand Management, 32: 233-250.

Central Pollution Control Board (2001). Parivesh: Newsletter, Ministry of

Environment and Forests, Delhi.

_____(2002). Toxic Air Pollutants,Parivesh: Newsletter, Ministry of Environmentand Forests, Delhi.

Cropper, M.L., Simon, N.B., Alberini, A., Arora, S., Sharma, P.K. (1997). The

Health Benefits of Air Pollution Control in Delhi, American Journal of

Agricultural Economics , 79: 1625-1629.

CSE (1997) Death is in the Air, Down to Earth, Center for Science and

Environment.

Dave, J. M. (2001). Air Quality Management - Dr. Nilay Chaudhury MemorialLecture, Central Pollution Control Board, Delhi.

\24