Review Article

REVIEW OF OILFIELD CHEMICALS USED IN OIL AND GAS INDUSTRIES

ABSTRACT

The petroleum industry includes the global processes of exploration, extraction, refining,
transportation and marketing of natural gas, crude oil and refined petroleum products. The oil
industry demands more sophisticated methods for the exploitation of petroleum. As a result, the
use of oil field chemicals is becoming increasingly important and has received much attention in
recent years due to the vast role they play in the recovery of hydrocarbons which has humongous
commercial benefits. The three main sectors of the petroleum industry are Upstream, Midstream
and Downstream. The upstream deals with exploration and the subsequent production (drilling of
exploration wells to recover oil and gas). In the Midstream sector, petroleum produced is
transported through pipelines as natural gas, crude oil, and natural gas liquids. Downstream
sector is basically involved in the processing of the raw materials obtained from the upstream
sector. The operations comprises of refining of crude oil, processing and purifying of natural gas.
Oil field chemicals offers exceptional applications in these sectors with wide range of
applications in operations such as improved oil recovery, drilling optimization, corrosion
protection, mud loss prevention, drilling fluid stabilization in high pressure and high temperature
environment, and many others. Application of a wide range of oilfield chemicals is therefore
essential to rectify issues and concerns which may arise from oil and gas operational activities.
This Chapter intends to highlight some of the oil field chemicals and their positive applications
in the oil and gas Industries.
Keywords: Oil field chemicals, Petroleum, Enhance oil Recovery, Demulsifiers, Corrosion
1. INTRODUCTION

The oil and gas provide more 60 percent of their daily energy needs of world. It is considered the

biggest sector in term of dollar value and is the highest employer of labour in the world. They are

so dynamic they contribute a significant amount towards national GDP. Nevertheless the Oil

and gas industry is extremely effective and still experiencing enormous growth. The annual

global energy consumption is estimated to be over 30 billion barrels predominantly by the

industrialized nations. Oil and gas are vital to many industries and for civilization as it is the

indispensable energy source for transportation and chemical production. Its consumption is 32%

for Europe and Asia, 53% for Middle East, 44% for South and Central America, 41% Africa,

1
40% for America and 25% for United states of America. Natural gas is increasingly used for

power generation as utilities look to switch to lower-emissions fuels, gas will overtake coal as

the world’s second-largest fuel in about a decade. Numerous issues arise which relates to

Production chemistry which may be due to the physical and chemical changes in well stream

fluids as they are conveyed from the reservoir via the processing system. The fluids from the

wells usually contains complex mixtures of hydrocarbons (Natural gas, condensates and crude

oil), and associated water. The mixture is transported from the reservoir through tubular string

and wellhead through the flowlines to the processing plant for proper separation of the different

phases. During the operations, change in temperature, pressure drop, and constant agitation will

impact on the efficiency of the overall operation which may or may not be predictable. During

the Downstream processing plant operation, the crude oil is transported to the refinery, the gas

will be processed, while the water is treated to remove contaminants: in most case the processes

can lead to additional problems. Most of these processes from the upstream to downstream

requires the application of chemicals for effective delivery operations.

1.2 OILFIELD CHEMICALS AND SOME OF ITS APPLICATIONS

Oilfield chemicals are chemicals used in petroleum production, processing and transportation.

They are applied in operations such as drilling, completing and producing oil and gas wells.

Relatively, the activities and operations in the oil and gas industry are reliant on the oil field

chemicals to accomplish definite functions in the wellbore or formation. These oilfield chemicals

include common inorganic salts, common organic solvents, transition metal compounds and their

complexes, water-soluble and oil-soluble solvents and several others.

The alterations that takes place in the well stream fluids make oil field chemicals imperative by

oil and gas plants.

2
1.2.1 Numerous oilfield chemicals used in the oil and gas industries includes:

• Corrosion inhibitors – reduce corrosion

• Scale inhibitors – reduce scaling

• Demulsifiers – speed up oil and water separation; dehydrates oil

• Water clarifiers–Clean up water before disposal.

• Hydrate inhibitors – Prevent ice-like hydrates

• Asphaltenes inhibitors – Prevent asphaltenes (large molecule) precipitation.

• Acid stimulations – removes acid soluble rocks and scale

• Drag reducers – improves flow through pipelines by reducing turbulence

• Sand control chemicals–reduce undesirable sand production from the wellbore.

• Napthenate inhibitors – stop precipitation of Ca/Na salt of naphthenic acid

• Wax inhibitors – prevent wax deposition

• Foamers – Reduces the density of fluids in hydrostatic heads

• Biocides - destroy microbes, prevents corrosion

• Hydrogen sulphide scavengers - react with toxic H2S gas, corrosion control

• Oxygen scavengers - – reduces oxygen levels, prevents O2 corrosion

1.3 Drilling fluids

Drilling fluids are combinations, mixture or blends of natural and synthetic chemical compounds

used to cool and lubricate the drill bit, clean the hole bottom, carry cuttings to the surface,

control formation pressures, and improve the function of the drill string and tools in the hole [1].

Drilling fluids can be broadly classified into two main categories: water-based drilling muds
3
(WBMs) and oil-based drilling muds (OBMs). A drilling mud is distinct type of drilling fluid

used for drilling deep oil wells. Some of the major functions of Drilling fluids includes

regulation of downhole formation pressures, overcoming the fluid pressure of the formation,

ensuring that the producing formation is not damaged, removal of drill bit cuttings from the

borehole, and helping to cool and lubricate the drill bit [2, 3]. There are some factors to consider

in the classification of drilling mud. These includes the kind of chemicals used in the preparation

or formulation of the drilling mud, the dispersing properties and a combination of additional

properties can be used to classify drilling muds as water-based mud (WBMs) contains or oil-

based muds (OBMs). The water based muds contain water as water as the continuous phase

while the oil based mud contains oil as the continuous phase.

Due to the ability of potassium (K+) to bind to clay surfaces and impart great level of stability to

shales which are exposed to drilling fluids by bits, it is used in drilling water sensitive shales.

More also, the ions also aid to bind the cuttings together thus reducing its dispersion to smaller

particles. Potassium can be obtained from the following: Potassium chloride (KCl), potassium

acetate (CH3COOK), potassium carbonate (K2CO3), potassium hydroxide (KOH) and potassium

salt of partially hydrolyzed polyacrylamide (PHPA).

Different types of polymers are employed for rheological control, these includes xanthan gum

and PHPA. Chemicals such as combinations of starch and polyanionic cellulose (PAC),

Carboxymethyl starch, hydroxypropyl starch, carboxymethyl cellulose (CMC) are employed as

fluid loss control. Sodium chloride (NaCl) is main constituent of salt water muds, starch and its

by-products are used for fluid loss control, and xanthan gums for hole cleaning are among the

few additives that are effective for salt water muds.

4
In offshore drilling, sea water mud which is WBM is used. Sodium hydroxide (NaOH) and

sodium carbonate (Na2CO3) are used due to the presence of Mg2+ and Ca2+ ions which causes

hardness. The ions are removed and precipitated as magnesium hydroxide (Mg(OH)2 and

calcium carbonate (CaCO3).

Fluids whose density varies with pressure during drilling operation are known as variable

density fluids. They usually have base fluids and elastic particles which are a copolymer of

styrene and divinylbenzene, a copolymer of styrene and acrylonitrile, or a terpolymer of styrene,

vinylidene chloride, and acrylonitrile [4].

Water-based mud (WBMs) have fundamental components such as Polyacrylamide,

carboxymethyl cellulose, Acrylamide copolymer, polypropylene glycol (PPG) [5].

Efficient lubricating properties are achieved by combining Glycol or glycerol with anionic and

cationic fluids which acts as inhibitor to swelling and dispersing of shales.

The viscosities of oil based muds (OBM) are commonly enhanced by using ethylene-propylene

elastomers and Polyolefins (PAOs) due to their excellent properties such as good viscosity and

pour point, biodegradable and being harmless to marine organisms are used in the formulation of

OBM [6, 7].

Numerous naturally occurring polymers are added to drilling fluids to prevent fluid loss. Most of

these polymers are susceptible to microbial degradation during drilling operations. Quaternary

ammonium salts are used mostly used to protect the additives from biodegradation and reduce

consumption rate during drilling deep wells. Bacterial control is also important in drilling fluids,

and other oil and gas operations [8]. Some of the structures of chemicals used for bacterial

control (bactericides) or biozides recommended for drilling fluids are shown in figure 1.

5
 O
H
N O S
NH
N N N
S
1H-pyrazole 1,2-oxazole 1,2-thiazole
O 1,2-benzothiazol-3(2H)-one
Cl
N (CH 2)7CH 3
S
Cl
4,5-dichloro-2-octyl-1,2-thiazol-3(2H)-one

Figure 1.. Structures of components of bactericides or biozides

Some chemicals like Hydrazine are used as corrosion control in drilling operations and

cementing due to its ability to remove oxygen. Such chemicals are called oxygen scavengers. A

good example of such chemical is hydrazine [9].

Because of the excellent properties of naturally occurring calcium bentonites, they are used to

enhance the viscosity of numerous drilling fluid. Their characteristics can be improved by

blending with sodium carbonate to upgrade its quality to sodium bentonite which has superior

viscosity performance characteristics. Alkylsilanes and phosphonates are used to modify the

dispersing properties [10].

1.4 Surfactants, Dispersants and Deflocculants

Surfactants (surface-active agent) are compounds that has the ability of lower surface tension

between two liquids, a gas and a liquid, or liquid and a solid. They can be natural or synthetic.

The presence of functional groups in the surfactants provide specific performance properties for

a plethora of valuable industrial and consumer uses.

6
A dispersant or a dispersing agent or a plasticizer is a surfactant added to a suspension, (usually a

colloid) to enhance the separation of particles and prevent settling. They can be a mixture of

one or more surfactants, with the aim of reducing oil-water interfacial tension.

Surfactants like Methyl-diethyl-alkoxymethyl ammonium methyl sulphate applied as

hydrocarbon solvent have properties that can extinguish foam. Other like Alkylpolyglucosides

(APGs) which are biodegradable can be added to polymer muds to reduce fluid loss, enhance

rheology and temperature resistance [11, 12].

A major characteristics of Chemicals used as Deflocculants is that they should have a low

molecular weight. The dispersant used in dispersing bentonite suspension are complexes of

tetravalent zirconium with some organic acids (citric, tartaric, malic, and lactic acids), and a

complex of aluminium and citric acid have proved to be good dispersants. Furthermore,

polymers composed of sodium styrene sulfonate and Organophilic clays can be treated with a

quaternary ammonium surfactant having an amide linkage [13, 14, 15]. Examples of such

surfactants are shown in Figure 2. They are a type of cationic surfactant that is significantly

biodegradable, that is easily broken down by microorganisms in the presence of oxygen.

Modified clay which are treated can be used in drilling fluids without apprehension of the

likelihood of the surfactant contaminating the environment.

O
CH3
+ O
CH 3 (CH 2)16 NH N
- CH3 CH3
Cl CH3 +
CH 3 (CH 2)16 NH N
-
Cl CH3

7
Figure 2 Quaternary ammonium surfactants

1.5 Cuttings, Junk and Filter Cake Removal

Chemicals like Barium sulphate are ground, filtered and suspended in drilling fluid to get rid

cutting beds. Cutting bed are deposits of small size drill cuttings that build at the lower side of

the wellbore when drilling horizontal wells. It is added to the drilling fluid and circulated in the

wellbore to remove the small cuttings or cuttings beds from the borehole and transports them to

the well surface. A mixture of Nitric and hydrochloric in a ratio 1: 3 can be used to dissolve

drilling equipment that is broken or stuck in hole. The dissolution of the metal is accelerated by

adding a mixture of containing 1.1 parts of sodium nitrate and 1.0 part of monoethanolamine.

Further addition of an alkali and polymer solution neutralises the acidic residue and then

converts the mixture into a drilling fluid [15, 16].

Circulation of the drilling fluid leads to the formation of a solid layer known as a filter cake on

the walls of the wellbore. Preflushes are special chemicals which contain surfactants usually

introduced to mitigate the problem of filter cake formation. An aqueous chemical wash solution

contains sulfonated bisulfite lignin, and a taurate, present in amounts of 0.1– 5% [17]. Examples

of taurates useful for preflushes are N-methyl-N-cocoyl taurate, N-methyl-N-palmitoyl taurate,

and N-methyl-N-oleyl taurate and their metal salts (Figure 3). They are obtained by the acylation

of N-methyl taurine with the corresponding long chain acids [18].

8
 O
R O
CH3
OH R
H N
N O
OH H3C S OH
S
O O
O

Figure 3. Acylation of N- Methyl-taurine.

1.6 Transport of Petroleum and its products

Pipelines are essential to the petroleum and gas industries for the transport of natural gas, crude

oil and refined products. Chemicals and additives are used to ease the conveyance of these

materials from one location to another. A lot of corrosives like Carbon dioxide (CO2) and

hydrogen sulphide (H2S), water emulsified in the crude oil, naphthenic acids are the main cause

of corrosion problems. They can also cause problems during refining, and processing [19].

Chemical additives are added to alleviate these problems. For example ammonia (NH4),

Hydrogen fluoride (HF) and occasionally carbon monoxide (CO) are added to natural gas to be

conveyed through pipelines. Treatment with alcohol like methanol reduces the naphthenic acid

content, these leads to ester formation.

Gas hydrates are undesirable compounds produced during production or transportation of natural

gas at low temperature and pressure. They are crystal-like or ice-like compounds of gas

molecules in water, which form at low temperature and high pressures. More attention is

attached to Gas hydrates in the petroleum industry due enormous problems they pose. Such

problems includes blockage of drilling equipment, flow restriction in pipelines, valves, or

9
production equipment in which wet gas or multiphase mixtures are transported over long

distances; as occurs in colder regions or on the seabed [20].

Gas hydrate can be prevented from forming by using moderately enormous amounts of lower

alcohols such as methanol, glycol, or diethylene glycol. The main problem with hydrate

formation arises in pipelines that transport natural gas, because they are solids and deposit.

Chemicals such as polyethylene oxide in its aqueous solution, alkylated ammonium,

phosphonium, or sulfonium compounds and amino acids or amino alcohols can be added into a

drilling fluid to inhibit and interfere with formation and growth of gas hydrates [21].

Odorizers are added to natural gas to let its presence to be perceived in the environment before it

reaches explosive levels. Few examples are ethyl mercaptan, diethyldisulphide and mixture of

ethylmercaptan, propylmercaptan and butlymercaptans. The most important compounds are

given in Figure 4.

SH
H3C SH H3C SH
H3C CH3
ethanethiol butane-1-thiol
CH3
2-methylpropane-2-thiol

CH3
H3C S
H3C S CH3 ethyl propyl sulfide
diethyl sulfide

Figure 4, Structures of additives used for Odorization

Many anionic, cationic and non-ionic surfactants are used to remove solid materials produced

during well drilling, polishing and gridding metals. Examples of such surfactants are

10
cetyltrimethyl ammonium chloride, dodecyl diphenyl oxide disulfonate, and soya bis[2-

hydroxyethyl]amine [22].

There are some parameter that should be put into consideration when heavy crude oils is being

transported. Some of these include velocity, viscosity, temperature, density, and pour point.

Chemical treatment of the heavy crude oil helps to activate the natural surfactants present in

them [23, 24]. The method of chemical treatment is more effective than heating or diluting crude

oils which have high viscosity. Carboxylic acids which are constituents of crude oils are the

surfactant’s precursors. Aqueous buffer solution of sodium hydroxide with sodium bicarbonate

or sodium is used for activation [24, 25]. During low temperature transportation, inorganic salts,

such as aluminium nitrate can be used in small quantities (30 ppm) are additional stabilizers for

the emulsion [26]. In addition to the surfactants used in low temperature transportation,

chemicals such as salts, sugars and glycerol can be added as freezing point depressant [27].

1.7 Pour Point Depressants and Chemical Inhibition

The wax content of some crude oils are very high and they tend to pose problem during their

transportation through pipelines especially in cold regions due to their high pour points.

Chemical inhibitors are nitrogenous complex mixtures used in oil production. There are different

classes of Inhibitors such as oil-soluble, water-soluble or dispersible. The basic functions of

chemical inhibitors is that they are film formers which protect the pipeline surfaces. A few

examples are shown the figure 5

11
 N
CH3
+
S N
N
H N
2-methyl-1,3-benzothiazol-1-ium
N N
H H
S 1H-benzotriazole
2-phenyl-1H-benzimidazole NH
H3C NH CH3
1,3-dimethylthiourea

Figure 5. The structure of Corrosion inhibitors used in oil production

1.8 Corrosion Inhibitors

The deterioration of a substance, especially metals or its properties due to their reaction with

interact with the environment is known as corrosion. Corrosion can lead to failure of

operational processes in the oil and gas. Plate 1. shows the effect of corrosion on metal pipes.

Plate 1. The effect of corrosion on metal pipes

Corrosion inhibitors are oilfield chemicals that control corrosion of all facilities used during

exploration and production of petroleum. They control internal and external corrosion of

12
downhole tubing and equipment, surface and sub-sea pipelines, pressure vessels and storage

tanks. Electrochemical corrosion of these facilities can lead to cracking and subsequent

equipment failure. Corrosion of iron in steel requires the presence of water and aqueous species

that can be reduced while the iron is oxidized. The presence of oxygen, acid gases like CO2, H2S

and other natural organic acids contained in the produced fluids also contribute to corrosion of

oil and gas facilities.

There are different categories of corrosion inhibitors such as passivating (anodic), Cathodic,

Vapour-phase or volatile, Film-forming. Film-forming corrosion inhibitors are generally used for

protection and fortification of oil, condensate and gas production lines. Application of

passivating corrosion inhibitors are rare in oil and gas production. They are mostly used in low-

salinity applications such as utility systems. When a passivating inhibitor is used, an unreactive

thin surface is formed on the metal which stops access of corrosive substances to the metal,

thereby inhibiting further corrosion. Examples of passivating corrosion inhibitors are: phosphates

and polyphosphates, tungsten, silicates, chromates, meta-, ortho-,and pyrovanadates (NaVO3,

Na3VO4 and Na4V2O7 respectively ) etc. several of the passivating inhibitors are metal anionic

species.

Phosphate corrosion inhibitors help maintain a mineral passivation layer on the inside of flint’s

pipes, protecting them from corrosion with little corrosion, chlorine disinfectant levels remain

stable. See plate 2.

13
Plate 2. Phosphate corrosion inhibitors in pipes

Cathodic inhibitors either slow the cathodic reactions itself or selectively precipitate on cathodic

areas to increase the surface impedance and limit the diffusion of reducible species. They are not

used in production operations but have been used in drilling fluids. An example of cathodic

corrosion inhibitors is zinc oxide which works by retarding corrosion by inhibiting the reduction

of water to hydrogen gas. Corrosion inhibitors are typically a blend of components like:

Phosphate Esters, Sulphur Compounds, Various Nitrogenous Compounds, Quaternary

ammonium salts and betains, Amidoamines and Imidazolines, Polyhydroxy and ethoxylated

amines/amidoamines, Amides other heterocyclic.

Chemistry of Cathodic Inhibitors

(i)
Inhibition of oxygen absorption and hydroxyl ions

H2O + ½O2 + 2e- 2OH-

14
The formation of OH- ions can be prevented either by removing O2 from the medium or by

decreasing the diffusion of O2 in the cathode. O2 is removed either by adding reducing agents

like Na2SO3, N2H4, etc

O2 + NH2-NH2 N2 + 2H2O

2Na2SO4 + O2 2Na2SO4

Salts of Zn, Mg or Ni are added to corroding medium to reduce the diffusion of O2 towards

cathode. These salts react with OH- ions at the cathode forming insoluble hydroxides which are

adsorbed at the cathode.

Plate 3. Migrating corrosion inhibitors and vapour-phase corrosion inhibitors

Vapour-phase corrosion inhibitors are organic compounds which adsorb onto surfaces of metals.

Examples are diethylamine phosphate, trimethylamine, dicyclohexylamine carbonate,

dicyclohexylamine nitrite etc. Plate 3 shows migrating corrosion inhibitors and vapour-phase

corrosion inhibitors.

15
Hydrogen sulphide and carbondioxide corrosion are better prevented by film-forming corrosion

inhibitors. The mode of operation is by adsorbing on the surface of the metal thereby forming a

protective layer that physically prevents corrosive chemicals from penetrating to the metal

surface. They are mostly organic amphiphiles i.e. surfactants that have a polar head group and a

hydrophilic tail (plate 4).

Plate 4. Surfactants with polar head and hydrophilic tail

The most common categories of surfactants used as film-forming corrosion inhibitors are

phosphate esters, various nitrogenous compounds like amine salts of carboxylic acids,

polyhydroxy and ethoxylated amine/amidoamines, amides etc; and sulphur compounds with

heteroatoms such as nitrogen. Biodegradable polyaminoacids have also been employed in

environmentally sensitive areas. Typical phosphate ester film-forming corrosion inhibitors:

O
HO O
HO P R1 O P O R2
O O
O P O O OH
R O R O R
n OH n n
mixed phosphate diesters
phosphate esters
Phosphate monoesters
P2O5 based

16
Figure 6. Corrosion and Scale Inhibitors

The two most expensive problems in the petroleum industries are corrosion and scale deposition.

This is because most of surfaces and equipment used in production, transport and refining

operations are corrodible. Oil field corrosion is associated with deposition conditions and

contact with oxygen. Iron sulphide or other solid particles can deposit on the metal surface and

prevent access by corrosion inhibitors. Corrosion inhibitors can be generally classified into the

groups:

(i) Amides and imidazolines

(ii) Salts of nitrogenous molecules with carboxylic acids, i.e., fatty acids and naphthenic

acids

(iii) Nitrogen quaternaries

(iv) Polyoxylated amines, amides, imidazolines, and

(v) Nitrogen heterocyclics.

The use of stainless steels have been used efficiently to combat hydrogen sulphide (H2S) and

carbon dioxide (CO2) corrosion, but these materials are susceptible to hydrochloric acid (HCl).

HCl is used in oil and gas production to stimulate the formation. Epoxide resins with aromatic

amines are used as coatings for internal corrosion of petroleum pipelines [28, 29]. Chemicals

employed as downhole corrosion inhibitors are polymers with high amine content like

polybutadiene. Also downhole metal surfaces in oil and gas wells are inhibited from corrosion

with a combination of vinyl monomer such as an unsaturated acid, acrylonitrile, vinylester or

N-inyl-2-pyrrolidone and mercaptan Figure 7.

17
 CH2
CH2
CH
HC O
O
N
O CH3

ethenyl acetate
1-ethenylpyrrolidin-2-one

vinyl monomers

Figure 7. Relevant vinyl monomers

1.10 Scale Inhibitors and Removal by Acid treatment

In the petroleum industries, activities such as production and transport are usually faced with

deposition of scales. This often occurs when there a change in temperature during injection

operations and the solution becomes supersaturated. A mixture of two chemicals which easily

precipitates usually leads to scale formation. A typical example is a mixture of hydrogen fluoride

with a solution containing calcium ions. Scales may contain calcium carbonate, barium sulphate,

gypsum, strontium sulphate, iron carbonate, iron oxides, iron sulphides, and magnesium salts.

When a substance that react with probable Scale-forming substances is added stop or to subdue

crystal formation it can lead to Inhibition of Scales. Scale formation is the deposition of

sparingly soluble inorganic salts from aqueous solutions. In addition, there is another type of

scale containing metal ions in which the anions are organic carboxylates or naphthenates. When

scales are formed, they block pore throats in the near-wellbore region or in the well causing

formation damage and loss of productivity. Scales forms along the production pipe casing a

18
reduction in the internal diameter thereby blocking flow; scales can also form in processing

facilities.

Scale inhibitors are generally categorized as organic or inorganic. Examples of inorganic scale

inhibitors are condensed phosphate, such as polymetaphosphates or phosphate salts. Organic

scale inhibitors includes polyacrylic acid (PAA), phosphinocarboxylic acid, sulfonated polymers,

and phosphonates. The phosphonates are good at high temperatures, while the sulfonated

polymers perform better at low temperatures [30, 31]. Most scale removers or inhibitors such as

acids which are introduced downhole to remove scales are corrosive to the production tubing

and casing liners. The addition of Inhibitors to the stimulation fluids minimizes the corrosion of

tubing and casing liners.

Types of scales:

There are different scales encountered in the oil and gas industry. They include

• Calcium carbonate

• Sulphate salts of calcium, strontium and barium

• Sulphide scales – iron (II), zinc, and lead (II) salts

• Sodium chloride

Calcium carbonate scale: Although calcium bicarbonate is water soluble, calcium carbonate is

not. Formation water usually contains bicarbonate ions as well as calcium ions. Calcium

carbonate can deposit.

2HCO3- ↔ CO32- + H2O + CO2

19
If pressure drops, the equilibrium moves to the right with more CO2 forming. As a result, more

carbonate ions are formed. At some point, the concentration of carbonate ions may be high

enough that calcium carbonate precipitates.

Ca2+ + CO32- → CaCO3(s)

Sulphate scales are usually formed when formation water and injected seawater mix. Also, two

different non-scaling well fluids may mix in topside flow lines and cause topside scale problem.

Scale formed from sulphide compounds are less common than carbonate and sulphate scales

but are still a major challenge in the oil and gas industry if not controlled. Some hydrogen

sulphide is present in formation waters. For oil wells, the bulk of this comes from the activity of

sulphate-reducing bacteria (SRBs) on the sulphate ions in the injected seawater.

H2S + H2O ↔ H3O+ + HS-

HS- + H2O ↔ H3O+ + S2-

Formation water may sometimes be saturated with sodium chloride. As the temperature of

produced water decreases, sodium chloride may precipitate out. Water flash-off into the gas

phase as pressure decreases during production will concentrate solutions of sodium chloride,

which may eventually also lead to halite (sodium chloride) precipitation. Scales can also be

layered and of mixed composition, for example, containing both carbonate and sulphate scales, at

the appropriate field conditions. Formation water generally comprises of calcium carbonate

which is insoluble and calcium bicarbonate which is soluble. Both are present in their ionic

forms. Plate 5 shows examples of scales.

20
Plate 5 Scales

2.0 Enhanced Oil Recovery

The conventional crude oil production method can recover 30 – 40% of oil reserves. Enhanced

Oil Recovery (EOR) is used to recover the rest of the crude oils from the reservoir. The methods

used in Enhanced oil recovery involves the use of chemical and gas floods, steam, combustion,

and electric heating.

Chemical floods involves the injection of definite chemicals which include polymers,

surfactants, and alkalis, most of these chemicals are often combined.

21
Alkyl-aryl sulfonates have been known as good for EOR by surfactant flooding but for waxy

crudes, the use of olefins greater than C10 are used for the alkylation of xylene sulfonate or

toluene sulfonate, in contrast to conventionally used alkyl-aryl sulfonates, which generally have

a narrow range of olefin carbon number, such as C12-xylene sulfonate [32]. Some examples of

olefinic sulphonic acid surfactant (linear or branched) are shown in figure 8

H3C (CH)m CH (CH)m SO 3H H3C (CH)m CH (CH)m SO 3H

H3C (CH)x CH (CH)y CH3 H3C (CH)x CH (CH)y CH3

OH SO 3H
O(CH 2CH 2O) m(CHCH 2O) nH (CH)m

H3C (CH)x CH (CH)y CH3

H3C (CH)x CH (CH)y CH3

Sulphoalkylated phenol surfactants

Figures 8. Chemical structure of sulphonalkylated phenol surfactants

Field trials revealed that the injection of silicone on a gas production was beneficial and the gas

production tripled and was sustained for at least six months [33].

Hydrochloric acid (6 –30%,) is frequently used, sometimes also with hydrofluoric acid and

sometimes surfactants like isononyl phenol added [34]. The environment is then made acidic

thus converting the sulfonates into sulfonic acid, which has a lower interfacial tension (IFT)

toward oil, thus having a better efficiency in forcing out oil compared with the neutral, aqueous

solutions of sulfonates. Cyclic injection can be applied and sulfuric acid has also been used for

acid treatment. Injecting additional aqueous lignosulfonate increases the efficiency of a sulfuric

22
acid treatment. A combination of Hydrochloric acid with chlorine dioxide can be used as a

treatment fluid in water injection wells that get impaired by the deposition of solid residues [35,

36].

2.1 Demulsifiers

Emulsions are colloidal dispersion, droplets of one phase dispersed in a second phase. Crude oil

is almost always produced as a water-in-oil emulsion, i.e. water droplets stabilized in a

continuous crude oil phase plate 6 is representation of types emulsion. . Free produced water

may also be present depending on the water cut. The water and dissolved salts in the emulsion

must be separated out before the oil is accepted for export, further transportation or treatment at

the refinery. This process is called demulsification or dehydration. There is a specified maximum

value of water content in crude before it is sold. characteristically, the desired maximum water

content is in the range of 0.2-0.5%. the water separated from the water-in-oil emulsion usually

contain dispersed oil as an oil-in-water emulsion. This also need treatment called de-oiling.

23
Plate 6 Representation of types emulsion

Emulsions are formed due to turbulence in the production tubing and pipeline when passing

through chokes as the wellhead. Demulsifiers are added to resolve the problem of emulsions

usually encountered in the oil and gas industries. Depending on the water phase, the

concentration of the added demulsifier is in the range of 5-500 ppm. Sufficient mixing is

required to get the demulsifier to the oil-watr interface. In addition, time must be allowed for the

coalesced droplets to phase separate. Any emulsion that is not broken is known as slop. A

prerequisite for good demulsification is that the oil-water emulsion should be free of gas. If the

crude oil contains significant amount of gas, the formation of gas bubbles will cause unnecessary

agitation restricting the ability of the chemical demulsifier to produce a clean interface. Gas may

be beneficially removed upstream in a gas separator.

On breaking the emulsion, the bulk of the water would be separated and the oil ready for further

transportation and processing at the refinery. Residual oil is still contained in the water separated

out at the processing facilities in the form of an oil-in-water emulsion or reverse emulsion. The

oil can be separated from the water using water clarifiers, de-oilers or reverse emulsion breakers.

The existence of water-in-oil emulsions usually causes corrosion and the growth of microbes in

the water-moistened parts of the pipelines and storage tanks.

24
Prior to refining operation, crude oils are usually desalted by emulsification with fresh water,

followed by demulsification. This is because Crude oils with high salt contents might lead to

breakdown and corrosion during refining, and an emulsion breaker, or demulsifier, is used to

break the emulsion at the lowest possible concentration, to completely separate the water and

decrease the salt content to a lowest concentration.

In crude oil production, demulsifiers are usually injected at the processing facilities before the

separator. Emulsions that are slowly resolved need adequate time to separate. The fluids are

hotter upstream, thus will result in faster emulsion resolution. Often, a range of demulsifiers and

blends are taken to the process plants and tested by trial and error. Oils with a high viscosity hold

up more and larger water droplets. Lowering the viscosity increases both the rate at which

droplets settle and the mobility of water droplets, the speed at which they coalesce and separate

out.

Over the years, oilfield chemical manufacturers have developed an ever-increasing range of

products in attempts to destabilize emulsions. Water-in-oil demulsifiers are polymeric non-ionic

chemicals with molecular weight of about 2,000-50,000. Anionic and cationic polymers can be

used depending on the emulsion-stabilizing chemicals in the feed-stream or wetting agents.

Examples of water-in-oil demulsifiers are polyalkoxylates of polyols, polyurethanes, vinyl

polymers, polysilicones, ester derivatives, alkylpenol-aldehyde resin alkoxylates etc. blends of a

demulsifier and a polyalkylene glycol ether have been claimed to give better emulsion breaking.

Most classes of water-in-oil demulsifiers are oil-soluble and are deployed as solutions in

hydrocarbon solvents. Also, mixed aromatic/low alcohol solvents are commonly used. From the

above listed examples, many categories of demulsifiers contain polyalkoxylate chains.

25
The Polyalkoxylates can be produced by ring-opening of the oxides of ethylene, propylene,

butylene or tetrahydrofuran using a base an amine or alcohol. Polyoxyethylene chains are very

hydrophilic, polypropylene oxide chains are mildly hydrophobic while polybutylene chains are

very hydrophobic. Thus, one can make a range of products using the same alcohol or amine base

with varying side chains. A number of polyalkyleneamines are obtainable commercially. They

can be derivatized with several quantities of ethylene oxide and propylene oxide to produce

branched demulsifiers. Examples of polyethyleneamines are ethyleneamine (EDA),

diethylenetriamine (DETA), triethylenetriamine (TETA) and higher polyethyleneamines. Studies

on DETA-based demulsifiers showed that roughly equal amounts of Ethylene oxide and

propylene oxides in the side chains gave optimum performance

Products based on ring-opening reactions of epoxydized fatty acid esters with amines, diamines

or polyamines after subsequent alkoxylation have shown to have excellent breaking effect even

at low concentrations. Figure 9. shows the structure of Diethylenetriamine Demulsifiers which

contain amide groups can be produced by reacting DETA with fatty acids (adipic acid) followed

by alkoxylation.

NH
NH 2 H2N

NH
H2N NH2
N-(2-aminoethyl)ethane-1,2-diamine

Figure 9. Structure of Diethylenetriamine (DETA)

26
Some demulsifiers can also have secondary function. A typical example is the salt of an alkyl

sulphonic acid and an alkylamine which is an efficient demulsifier but then possesses corrosion

inhibiting properties. Figure 10 shows methacrylic monomers used as demulsifer.

CH3
O CH3 O

H2C C CH2 N H2C N

O CH3 O

CH3 CH3 CH3

Dimethylaminoethyl methacrylate Diethylaminoethyl methacrylate

O CH3
O
H2C CH3
NH N H2C N
CH O
CH3 CH3
CH3
Dimethylaminopropyl methacrylate Diethylaminoethyl acrylate

H2C CH
+
N NH2

H2C CH2 Diallylamine

N,N-diallylcyclohexylamine

Methacrylic monomers for demusifiers

Figure 10. Structures of Methacrylic monomers

2.3 Oil Spill Treating Chemicals

There are numerous chemicals used in treating oil spills. They are grouped into the following

categories: (i) solidifiers (ii) demulsifying agents (iii) surface-washing agents and (iv)

27
dispersants. These chemicals should possess characteristics such as a long shelf life,

environmentally friendly, non-toxic, non-polluting, biodegradable, highly active and

noncorrosive. Chemicals such as an oil-soluble, oxyethylated alkyl phenol, an alkyl phosphate of

a higher fatty acid alcohol, and a fatty acid amide of diethanol amine, are suitable for removing

crude oils and petroleum products from water surfaces [37]. Copolymers of dienes and p-

alkylstyrenes are used as dispersants. Corexit 9580 is a mixture of a sorbitan monoester of an

aliphatic monocarboxylic acid, a polyoxyethylene adduct of a sorbitan monoester, a water-

dispersible salt of a dialkyl sulfosuccinate, a polyoxyethylene adduct of a sorbitan triester or a

sorbital hexaester of an aliphatic monocarboxylic acid, and propylene glycol ether as solvent

[38]. It shows little fish toxicity, low dispersiveness, and effective rock cleaning capability.

3.0 Considerations For Application of Oilfield Chemicals

Oilfield chemicals are generally used in operational processes of the oil and gas industry to

achieve specific purposes. These functions can be broadly categorized into three (i) Integrity

management (ii) Flow assurance and (iii) Process optimization.

(i) Integrity management of oil and gas facilities: The major purpose of applying oilfield

chemicals is to prevent all forms of corrosion. This in turn safeguards the facilities to advert

failure during exploration, production and processing of crude oil and natural gas. Facilities

concerned are well tubing, pipes and pipelines, storage tanks, separators etc. The class of oilfield

chemicals employed to maintain integrity of these facilities include corrosion inhibitors, oxygen

scavengers, hydrogen sulphide scavengers, sand control chemicals and biocides.

28
(ii) Flow assurance: This refers to designs, strategies and principles ensuring successful and

economical flow of hydrocarbon stream from reservoir to the point of sale i.e. ensure unrestricted

flow of process fluids. Examples of oilfield chemicals employed in oil and gas operations to

obtain maximum flow assurance are Scale Inhibitors, hydrate inhibitors, wax inhibitors,

asphaltene inhibitors, naphthenate inhibitor and acid stimulation.

(iii) Process optimization: This refers to the discipline of process adjustment to optimize some

specific set of parameters without violating some constraint. It is commonly done to minimize

cost, maximize throughput and ensure efficiency of process operations. Examples of oilfield

chemicals to fit into this category are demulsifiers, water clarifiers, defoamers, drag reducers etc.

Water Clarifiers which are also known as De-oilers are applied after demulsifiers and subsequent

separation, clean up water before discharging to sea or other water bodies.

Environmental Restrictions: Both the developed and developing nations of the world have

guidelines, protocols and regulations on the classification of chemicals based on the hazards and

risks they portend on the users as it relates to health and safety. Operators in the oil and gas

industries should consider environmental impact of the chemicals. These indispensable and vital

information are contained in the Material safety Data Sheets (MSDS) for the chemical which

must accompany shipment of all potentially hazardous products according to laid down laws and

regulations. In general, it is noted that the UK and US are strict while the Africa and other third

world countries are not so strict with environmental regulations.

29
4.0 CONCLUSION

The energy landscape is changing worldwide. Consequently to deliver global demand for energy,

operators of the oil and gas industry has put unparalleled programmes of different extraction

methods in the search for and development of old and new hydrocarbon reserves. Activities such

as enhanced oil recovery, drilling of complex deepwater wells, hydraulic fracturing exploiting

resources and innovative technologies which employ the use of oilfield chemicals have resulted

in economical sustainability of crude oil and natural gas. The oil and gas process plant is

incomplete without the use of chemicals in its operations. Varying problems are encountered

during exploration, production and processing activities. Oilfield chemicals are produced to

surmount, minimize and reduced to barest minimum most of the challenges encountered during

oil and gas operations. The use of oilfield chemicals in exploration, production and processing of

crude oil and natural gas is vital to operating at lower costs, obtaining maximum efficiency,

process optimization and enhanced productivity in the oil and gas industry.

30
REFERENCES

1. Johannes KF. Petroleum engineer's guide to oil field chemicals and fluids, 2012.

2. Brazzel RL. Multi-component drilling fluid additive, and drilling fluid system
incorporating the additive. US Patent 7 635 667, assigned to Ambar Lonestar Fluid
Services, LLC (Layfayette,LA), December 22, 2009.

3. Melbouci M, Sau AC. Water-based drilling fluids. US Patent 7 384 892, assigned to
Hercules Incorporated (Wilmington, DE), June 10, 2008.

4. Ravi KM, Whitfill DL, Reddy BR. Methods of drilling wellbores using variable density
fluids comprising coated elastic particles. US Patent 7 482 309, assigned to Halliburton
Energy, 2009.

5. Patel BB, Muller GT. Compositions comprising an acrylamide-containing polymer and

process therewith. EP Patent 728 826, assigned to Phillips Petroleum Co., August 28,
1996.

6. Ashjian H, Peel LC, Sheerin TJ, Williamson RS. Non- toxic biodegradable well fluids.
WO Patent 9 509 215, assigned to Mobil Oil Corp., April 06, 1995.

7. Jones CK, Acker DB. Oil-based drilling muds with increased viscosity. EP Patent 922
743, assigned to Nalco Exxon Energy Chem. L, June 16, 1999.

8. Rastegaev BA, Andreson BA, Raizberg YL. Bactericidal protection of chemical agents
from biodegradation while drilling deep wells. Stroit Neft Gaz Skvazhin Sushe More,
1999; (7–8), 32–34.

9. Sikora, D., 1994. Hydrazine – a universal oxygen scavenger (hydrazyna – niwersalny

inhibitor korozji tlenowej w pluczkach wiertniczych). Nafta Gaz (Pol) 50 (4), 161–168.

10. Kondo, M., Sawada, T., 1996. Readily dispersible bentonite. US Patent 5 491 248,
assigned to Hojun Kogyo Co. Ltd., February 13, 1996.

11. Fabrichnaya, A.L., Shamraj, Y.V., Shakirzyanov, R.G., Sadriev, Z.K., Koshelev, V.N.,
Vakhrushev, L.P., Tavrin, A.E., 1997. Additive for drilling solutions with high foam
extinguishing properties – containing specified surfactant in hydrocarbon solvent with
methyl-diethyl-alkoxymethyl ammonium methyl sulphate. RU Patent 2 091 420, assigned
to Etn Co. Ltd., September 27, 1997.

31
12. Nicora, L.F., McGregor, W. M. Biodegradable surfactants for cosmetics find
application in drilling fluids. In: Proceedings Volume, Iadc/SPE Drilling Conf. (Dallas,
3/3–6/98), 1998, pp. 723– 730.

13. Grey, R. A. Process for preparing alternating copolymers of olefinically unsaturated

sulfonate salts and unsaturated dicarboxylic acid anhydrides. US Patent 5 210 163,
assigned to Arco Chemical Technol. Inc., May 11, 1993.

14. Peiffer, D. G., Bock, J., Elward-Berry, J. Thermally stable hydrophobically associating
rheological control additives for water-based drilling fluids. CA Patent 2 055 011,
assigned to Exxon Research & Eng. Co., May 07, 1993.

15. Burrafato, G., Carminati, S., 1994. Aqueous drilling muds fluidified by means of
zirconium and aluminium complexes. EP Patent 623 663, assigned to Eniricerche SPA and
Agip SPA, November 09, 1994.

16. Dolganskaya, S.I., Sharipov, A.U. Removal from hole of junk and stuck drilling
equipment –by dissolving latter with mixture of nitric and hydrochloric acids with added
sodium nitrate and ethanolamine. SU Patent 1 782 271, assigned to W Sibe Deep Pros
Dril Des., December 15, 1992.

17. Dealy, S. T., Chatterji, J. Chemical wash compositions for removing drilling fluids.
US Patent 7 662 752, assigned to Halliburton Energy Services, Inc. (Duncan, OK),
February 16, 2010.

18. Walele, I. I., Syed, S. A. Process for making N-acyl taurides. US Patent 5 434 276,
assigned to Finetex, Inc. (Elmwood Park, NJ), July 18, 1995.

19. Bromley, M. J., Gaffney, S. H., Jackson, G. E. Oilfield emulsion control, techniques and
chemicals used to separate oil and water. In: Proceedings Volume, Volume 3, Inst.
Corrosion UK orrosion 91 Conf., Manchester, UK, October 22–24, 1991.

20. Dahlmann, U., Feustel, M. Corrosion and gas hydrate inhibitors having improved water
solubility and increased biodegradability. US Patent 7 341 617, assigned to Clariant
Produkte (Deutschland) GmbH Sulzbach, DE, March 11, 2008.

21. Kannan, K., Punase, A. Low-dosage, high-efficiency, and environment-friendly

inhibitors: a new horizon in gas hydrates mitigation in production systems. In: SPE
International Symposium on Oilfield Chemistry, 20–22 April 2009, no. 120905-MS, SPE,
Society of Petroleum Engineers, The Woodlands. Texas, pp. 1–8.

32
22. Rose, G.D., Tetot, A.S., Doty, P. A. Process for reversible thickening of a liquid. GB
Patent 2 191 716, December 23, 1987.

23. Gerez, J.M., Pick, A. R. Heavy oil transportation by pipeline. In: Proceedings
Volume, Volume 2 1st Asme et al Int. Pipeline Conf., Calgary, Can, June 9–13, 1996, pp.
699–710.

24. Padron, A. Stable emulsion of viscous crude hydrocarbon in aqueous buffer solution and
method for forming and transporting same. EP Patent 672 860, assigned to Maraven SA,
September 20, 1995.

25. Rivas, H., Acevedo, S., Gutierrez, X. Emulsion of viscous hydrocarbon in aqueous
buffer solution and method for preparing same. GB Patent 2 274 254, assigned to
Intevep, July 20, 1994.

26. Rodriguez, D., Quintero, L., Terrer, M.T., Jimenez, G.E., Silva, F., Salazar, P. J.
Hydrocarbon dispersions in water. GB Patent 2 231 284, November 14, 1990.

27. Gregoli, A.A., Olah, A. M. Low-temperature pipeline emulsion transportation

enhancement. US Patent 5 156 652, assigned to Canadian Occident Petrol. Ltd., October
20, 1992.

28. Camberlin, Y., Grenier, J., Poncet, S., Bonnet, A., Pascault, J.P., Sautereau, H.
Utilization of polymer compositions for the coating of surfaces, and surface coating
containing such compositions (utilisation de compositions de polymeres pour le
revetement de surfaces et revetement de surfaces comprenant ces compositions). EP Patent
931 819, assigned to Inst. Francais Du Petrole, July 28 1999.

29. Petersen, H., Martens, J., Harms, W., Kramer, U. Process for avoiding the formation
of condensates, hydrates or ice in the decompression of natural gas stored in salt caverns
(verfahren zur vermeidung der bildung von kondensaten, hydraten oder eis bei der
entspannung von in salzkavernen gespeichertem erdgas). DE Patent 3 927 905, assigned
to Energieversor Weser Ems A, February 21, 1991.

30. Talbot, R.E., Jones, C.R., Hills, E.. Scale inhibition in water systems. US Patent 7 572
381, assigned to Rhodia UK Limited, Hertfordshire, GB, August 11, 2009.

31. Viloria, A., Castillo, L., Garcia, J.A., Biomorgi, J. Aloe derived scale inhibitor. US
Patent 7 645 722, assigned to Intevep, S.A., Caracas, VE, January 12, 2010.

32. Lakatos, I., T´oth, J., Lakatos-Szab´o, J., Kosztin, B., Pal´asthy, G., H. W¨oltje,.
Application of silicone microemulsion for restriction of water production in gas wells. In:

33
 Proceedings Volume, SPE 13th European Petroleum Conference, Aberdeen, Scotland,
U.K., October 29–31, 2002.

33. Gorodnov, V. P., Ryskin, A.Y., Pavlov, M. V. Increasing oil extraction from stratum – by
pumping- in hydrochloric acid solution or its mixture with hydrofluoric acid or
ammonium fluoride, followed by pumping aqueous solution or surfactant. SU Patent 1 795
092, assigned to Giprovostokneft Des. Inst., February 15, 1993.

34. Abdulmazitov, R.G., Muslimov, R.K., Zakirov, A. F., Khajretdinov, F. M. Oil

recovery from carbonate oil-bearing seam – involves cyclic injection of acid solutions of
increasing concentrations after reduction of seam pressure. RU Patent 2 073 791,
assigned to Tartar Oil Inst., February 20, 1997.

35. Cavallaro, A., Curci, E., Galliano, G., Vicente, M., Crosta, D., Leanza, H. Design of an
acid stimulation system with chlorine dioxide for the treatment of water-injection wells.
In:Proceedings Volume, 7th SPE Latin Amer. & Caribbean Petrol. Eng. Conference,
Buenos Aires, Argentina, March 25–28, 2001.

36. Braden, M.L., Allenson, S. J. Method for separating liquid from water using amine
containing polymers. US Patent 5 021 167, assigned to Nalco Chemical Co., June 4,
1991.

37. Chaplanov, P.E., Chernikov, A.D., Mironov, O.G., Semanov, G.N., Svinukhov, A.G.,
Yaremenko,A.G., et al., Removing oils and petroleum products from water surfaces –
using mixture of oxyethylated alkyl- phenol, alkyl-phosphate and fatty acid diethanolamine. SU
Patent 1 325816, October 15, 1992.

38. Canevari, G.P., Fiocco, R.J., Becker, K.W., Lessard, R. R. Chemical dispersant for
oil spills.US Patent 5 618 468, April 08, 1997.

34