Study on the Application of Biocides in the Seawater Cooling System and Their Killing Effect in

the Laboratory (Xie et al, 2017)

 The main ingredients of seawater are Na+, Cl-, Mg2+, Ca2+, K+, HCO3-, SO42-, Br-, etc. The mass
fraction of salt in the general seawater is of 3% to 3.5% (the salt content is 30000 to 35000
mg/L).
 ↑ Salt content  ↑ Macroorganisms & Microorganisms  ↑ PROBLEMS
Problems: Corrosion, Scaling, Biological Growth and Adhesions to Seawater Cooling System,
Salt Fog Spray Problem
 Sodium hypochlorite (NaOCl) from seawater electrolysis  Chlorine Generator:
o Active chlorine (HClO, ClO-, Cl2) produced by a special electrode to electrolyze sodium chloride
(NaCl) solution or the seawater
o Residual chlorine content is maintained to be greater than 0.1 mg/L
o Chlorine is used appropriately as biocide when the pH of the cooling water: 6.57.0.
 The killing ability of chlorine decreases when the pH is high.
 Usually, the pH of the cooling water is mostly 7.58.5, and the killing effect of chlorine is
poor.
 Hypochlorite under acid condition is not stable and decompose rapidly. Slight overstability
hypochlorite is produced in the presence of caustic soda in the electrolytic cell.
o Sodium hypochlorite (NaOCl) is a strong oxidizer, which can oxidizing the enzymes in
the body, make the breathing system of the fouling organisms produce chemical
damage, or make the attachment organs (chassis and filopod, etc) of fouling
organisms shrink destroy cell wall, affect the nutrient to be absorpted, and make the
cell die.
o The advantages of adding the sodium hypochlorite produced by electrolyzing seawater:
 Large anti-fouling range (because it is a broad-spectrum biocide, can kill or expel away all
kinds of marine organisms, and the whole condenser seawater cooling system can be anti-
fouling safely)
 No pollution to the environment (because the continuous dosing method is adopted and
small amount can maintain to be added, and the marine organisms don't be adhered. its
harm to human body and the environment is weak at low concentration, and its active
ingredient is easy to be biodegradation, absorption and chemical reaction, and the residual
chlorine concentration decreases to 0 fast after dosing is stopped)
 Convenient daily management (because the technology has been very mature and the
system operation is fully automatic)
 Safe and reliable (the whole process completes in a closed system, and all the operation can
complete in the control room, hydrogen produced in the process of electrolysis is discharge
into the atmosphere through its storage tanks and there aren't any danger).
o The amount of chlorine consumed in all kinds of reaction is unable to be estimated. Even if the
water source is same, the usage varies with water temperature, chlorine dosage and contact
time, etc.
 The conventional water quality analysis result of the seawater from Zhuhai cross drain, provided by
Guangdong Power Grid Electric Power Science & Research Institute (Table 1.)

 The killing effect of NaOCl:

Mechanisms of Actions of Sodium Hypochlorite in Cleaning and Disinfection Processes

 The effectiveness factors of sodium hypochlorite in the cleaning and disinfection processes:
concentration of available chlorine and the pH of the solution.
 Hypochlorous acid (HOCI) is a weak acid and dissociates to the hypochlorite ion (-OCI) and
proton (H+) depending on the solution pH.
o HOCI is the active species in the germicidal action
o The concentration of -OCI is a key factor determining the cleaning efficiency.
 Summarized of advantages and disadvantages of NaOCl:

Besides, it also fulfills many requirements of the ideal disinfectant and has an excellent
cleaning action; furthermore, it is easily combined with some other cleaning elements and
detergents.
 Oxidizing Reactions:
o Both hypochlorous acid (HOCl) and the hypochlorite ion (-OCl) are strong oxidizing
agents. HOCl and -OCl have been reported to react with a wide variety of biological
molecules such as proteins, amino acids, peptides, lipids, and DNA at physiological pH
conditions.
o The CI atom in HOCl and -OCl behaves as Cl+, a strong electrophile, and combines with
a pair of electrons in parts of the substrate that have high electron densities.
o Among biological molecules, the C=C double bond, peptide bond (amide bond) , amino
groups, and thiol groups are susceptible to the electrophilic attack of Cl +. The CI atom is
reduced to the chloride ion (Cl-) as it accepts two electrons.
 Dissociation and equilibrium in aqueous solution:
o Hypochlorous acid (HOCl) is a weak acid (pKa=7.5, 25 0C) in aqueous solution and it
dissociates readily to -OCl and H+ depending on pH
−¿¿
+¿+OCl ¿
HOCl ↔ H
o In general, the pH of sodium hypochlorite solutions diluted to commonly used
concentrations at 50 to 200 mg AC/L ranged between 8.5 to10.
When pH 8.5-10 region  most of the chlorine exists as -OCl.
o When range pH 4-6  HOCI becomes the predominant species.
o When pH<4, HOCl is gradually converted to Cl2
−¿↔ Cl2 (aq )+ H 2 O ¿

HOCl+ H +¿+Cl ¿

o 3 different forms of chlorine exists (Cl2, HOCI, and -OCl), which are called free
available chlorine or free residual chlorine.
o However:
 The solubility of Cl2 (aq) in water is very low and readily escapes from the
solution.
 Also, in the neutral pH region (6.5 to 7.5),undissociated HOCl tends to be
decomposed at a relatively high rate and its concentration decreases gradually
during the storage period.
 On the other hand, dissociated -OCl is more stable in alkaline water, especially
at pHs > 10,
o Once free chlorine species reacts with ammonia or N-organo compounds to form
monochloramine, dichioramine, and trichioramine or a variety of organo-N-chloro
compounds, the term used is either combined chlorine, combined residual
chlorine, or combined available chlorine.
 The free and combined available chlorine in water are collectively described as total
residual (available) chlorine.
 Mechanisms of Germicidal Action
o The mechanism of the germicidal activity of HOCl or -OCl is due to:
 The inhibition of enzyme activity essential for the growth
 Damage to the membrane and DNA,
 And an injury to membrane transport capacity although it has not been fully
elucidated.
o HOCl stress is also suggested to generate common deleterious oxidative species which
can damage cellular components.
o On the other hand, the germicidal activity of a concentrated sodium hypochiorite
solution is based on its high pH (-OH action) and -OCl oxidation.

 Membrane permeability and Germicidal Activity

o Basically, ionized -OCl is not able to penetrate the microbial cell membrane because of
the existence of the lipid bilayer, a hydrophobic layer, of the plasma membrane.
Occasionally, some structures of the microbial cell wall also protect the cell from -OCl
penetration. Mycobacteria and corynebacterial possess a peculiar cell wall structure in
which the peptidoglycan is covalently linked to mycolic acids. The mycolic acids
represent a hydrophobic barrier to -OCl entry.
o Therefore, -OCl exerts an oxidizing action only form outside the cell (circle A).
o Steps of disinfection by -OCl:
  The rupture or disintegration of microbial cell wall and membrane appears to occur,
and then -OCl would inactivate functional proteins localized in the plasma
membrane. This is responsible for the poor germicidal activity of -OCl. On the other
hand, HOCl can penetrate the lipid bilayer of the plasma membrane by passive
diffusion.
 The penetration of HOCl is due to its electrical neutrality and to its modest
molecular size being comparable to that of water. This is true of neutral and small
molecules such as H2O2. As a result, HOCl can attack the microbial cell not only
from outside the cell (circle A') but also from inside the cell (circles B and C),
thereby accelerating the inactivation rate and enhancing the germicidal activity.

 Mechanism of Cleaning Action

o Role of OH-
 Sodium hydroxide (NaOH) is often added to sodium hypochlorite (NaOCl)
solution not only to strengthen the cleaning power, but also to stabilize free
available chlorine in the form of -OCl, and to reduce the corrosive effect of -OCl
on metal.
 -OH degrades fats (through saponification reaction), transforming them into
glycerol and sodium salts of carboxylic acids containing long chains of carbon
atoms (soap), which in turn reduce the interfacial tension of the remaining fat-
solution interfaces.

o Role of OCl-
 -OCl concentration is a major factor determining the actual AC concentration
required for the removal of protein (BSA), acidic polysaccharide (pectin), and
bacterial cells (Pseudomonas fluorescens) from hard solid surfaces (Al 2O3
surfaces)
 -OCl is available for the removal of biofilm. At first, bacteria along with
organic and inorganic molecules (proteins and polysaccharides) are adsorbed
on a solid surface forming a conditioning film. The conditioning film alters
induce the subsequent adhesion of microbial cells. The attached microbes
grow and produce polymeric substances that contribute to the anchorage of
the cells to the surface and serve to protect microbes from hostile
environments. Biofilm bacteria grown on various solid surfaces are 150 to
3,000 times more resistant to HOCl (pH 7) than are unattached cells.