Study on corrosion investigations in industrial effluents: a review
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Chhotu Ram
,
Bushra Zaman
Abstract
Corrosion affects the usefulness of metallic materials used in the construction of an effluent treatment plant (ETP). The present report investigates the corrosive and inhibitive properties of the chemicals present in the effluent of paper mill and distillery industries. Chemicals such as chloride, chlorophenols, phosphate, calcium, nitrite, and nitrate enhance corrosion, whereas the presence of sulfate, potassium, organic matter, and melanoidins (color) inhibits corrosion at an acidic pH level in distillery and paper mill effluents. A finding shows that pH level has an important role in increasing or decreasing the effect on corrosivity of effluents.
1 Introduction
Corrosion is the deterioration of a metal by its chemical or electrochemical reaction with its environment. The first report (Uhlig report) that drew attention to the economic importance of corrosion was published in 1949. During the 1970s, several corrosion-cost-related studies were conducted in various countries, e.g. United Kingdom, United States, Japan, etc. According to a recent US corrosion study (2011), the direct cost of metallic corrosion has been estimated at $300 billion per annum, representing 3.5% of the United States’ gross domestic product (Business Standard, 2012). In 2011, the estimated worldwide annual cost of corrosion was at $2.2 trillion. According to the American Waterworks Association (Virmani, 1998), the total annual direct cost due to corrosion from the drinking water and sewer systems was estimated at $36 billion in the United States. In Los Angeles, approximately 10% of the sewer pipelines were damaged due to sulfide corrosion, and the estimated costs for the rehabilitation of these pipelines were estimated at £400 million (Sydney et al., 1996). As per a Hindustan Zinc Limited (2016) report, India loses more than $100 billion in a year, which is about 4–5% of the total economy (Economic Times, 2016). Among the various industrial sectors affected by corrosion, losses in the utility sector are highest at ~35% in the United States. In the utility sector, the highest corrosion cost is from the rehabilitation of drinking water and sewer systems, as shown in Figure 1. Effluent treatment facilities in different industries are meant to reduce the pollution load as per the legal requirement. Hence, an effluent treatment plant (ETP) has various types of equipment that are affected by chemical and microbial corrosion. Various reports from different countries investigated the corrosivity in ETPs and the performance of materials for construction against corrosion so as to reduce the cost of corrosion (Perego et al., 1997a; Iversen, 2001a; Jabalera et al., 2006a; Wang & Singh, 2012). However, previous researches (Ram et al., 2014a,b; 2015a,b) on corrosion investigations on ETPs of paper mill and distillery effluents show that the various chemical constituents influence the corrosivity of industrial effluents. To the best of the authors’ knowledge, no systematic review has been reported on the corrosion-influencing factors in industrial effluents. Therefore, the present study carried out a systematic review about the corrosivity in ETPs, which ultimately helps in the selection of suitable materials.
Cost of corrosion in utilities sector.
2 Corrosion
Corrosion of metal occurs due to electrochemical reactions between metal and chemicals present in the surrounding media (Davis, 2000). Corrosion is a consequence of the natural process of a metal returning to its thermodynamic stable state, i.e. state with the lowest energy. Most metals, by nature, are found in their ionic state in the form of various oxides, hydroxides, sulfides, etc. The process of their conversion into useful metals and alloys, the metallurgical engineering, involves energy. Thus, most metals experience oxidation spontaneously, and hence, the formation of oxides/hydroxides/sulfides can take place. These compounds are loosely termed as rust, when observed under atmospheric conditions. The rust over a surface is weak and brittle in nature so the process of its formation affects the load-carrying capacity of the metal, thereby weakening the metallic machinery of the industry. The overall effect is the reduced life of the machinery or the process equipment.
In order to maintain electrical neutrality, metallic oxidation is always associated with a reduction reaction. The corrosion of metal occurs due to a set of oxidation and reduction reactions occurring either on different parts of a given metal acting as the anode and cathode, respectively, or on two dissimilar metals in contact with each other serving as the anode and cathode to complete the corrosion cell. Thus basic equations involved in corrosion may be considered, as given below (Hamilton, 1985):
Anodic reaction: metal dissolution
M↔ M2++2e− 1.1
Cathodic reaction:
Oxygen reduction occurs under aerobic and neutral pH conditions.
½ O2+H2O+2e−↔2OH− 1.2
Oxygen reduction occurs under aerobic and acidic conditions.
O2+4H++4e− → 2H2O 1.3
Hydrogen ion reduction occurs under anaerobic and acidic conditions.
2H++2e−↔2H↔ H2 1.4
In addition, chemicals present in the liquid media, e.g. Cl2, SO4−-, may also be responsible for other reduction reactions. Corrosion can be classified into two types: inorganic corrosion and microbiologically influenced corrosion (MIC) (Videla, 2007). Corrosion occurs between two elements, metal and electrolyte, and is known as inorganic corrosion, whereas MIC has three component systems, i.e. metal, electrolyte, and microorganisms. Microbes in microbial corrosion can initiate, facilitate, or accelerate the electrochemical reactions. However, the first type of corrosion also involves organic chemicals but no microorganisms.
Generally, corrosion is classified into eight categories depending on the morphological nature of attack and type of environment. Materials exposed to industrial effluents commonly have uniform corrosion, pitting corrosion, galvanic corrosion, intergranular corrosion, and erosion corrosion. One study (Ram et al., 2012) has reported the uniform corrosion on mild steel exposed to paper mill effluent. The chances of pitting are more at an acidic pH level, high chloride, a higher temperature of liquor, and media having oxidizing chemicals (Ram et al., 2015a). High velocity and rapid mixing in ETPs increase the erosive action of effluents. Thus, these conditions accelerate the rate of deterioration of metal due to relative movement and wearing action. Petroleum refinery wastewater was studied for the galvanic corrosion of steel coupled with copper, and increase in corrosion rate was observed with increasing MgCl2, anode/cathode area ratio, and temperature (Nosier, 2003).
3 Corrosion in effluent treatment plants
Most of the industries in the United States had built their treatment plants mandated by law in the mid to late 1970s. At that time, welded carbon steel, fiber glass reinforced plastic (FRP), precast concrete cylinder pipe, and reinforced concrete pipe were used. Nowadays, cast iron, steel, and stainless steels are widely used in the construction of ETPs (Tuthill & Avery, 1994; Tator, 2003). The ETP’s pieces of equipment, such as sludge scrapping equipment, grit removers, aerators, bar screens, weirs, bolting, biodigester, and piping, are heavily affected by corrosion. However, corrosive conditions of effluent vary from industry to industry. One of the earlier reports shows that mild steel and stainless steel, i.e. AISI 304 and AISI 316, are widely used in the construction of treatment plant used for purification of urban and industrial wastewater (Perego et al., 1997a)). Result indicates that Thiobacillus ferrooxidans in aerobic treatment increases uniform corrosion, while an anaerobic bacterium causes localized corrosion on AISI 304 during anaerobic treatment. In another work (Perego, 1997b), metal contamination occurs in stored food materials due to microbes and chemicals during biomass yeast production. Another report relates the direct cause of plant failures (reactor, equipment, piping, etc.) due to corrosion, fatigue, wear, etc. and suggested better maintenance and corrosion control programs (Fabiano & Currò, 2012).
One study cites uniform corrosion on mild steel and localized attack on stainless steel (AISI 304) coupons exposed to effluents from an anaerobic biodigester (Englert & Muller, 1996). In another study on stainless steel coupons that were exposed to five wastewater treatment plants, in AISI 304, pitting was observed in three plants, whereas in AISI 316, attack was shown in one plant. Duplex 2205 showed maximum resistance against localized attack (Iversen, 2001a). Iversen (2001b) evaluated the corrosion on AISI 304 exposed in the final stage of wastewater treatment plant. Corrosion resistance of stainless steel was also studied in synthetic solution of chlorides, nitrates, and sulfates. Petroleum refinery wastewater was studied for galvanic corrosion of copper with steel coupling, and the corrosion rate was observed to increase with the increase in MgCl2, anode/cathode area ratio, and temperature (Nosier, 2003). Kurissery et al. (2004) investigated the stainless steel AISI 304’s failure in synthetic solutions, and the corrosion-causing bacteria Pseudomonas sp., Bacillus sp., and sulfate-reducing bacteria (SRB) showed initiation of severe pitting. Another work investigated the corrosion of stainless steel pipes in the process water distribution system of a leather plant where MIC having manganese oxidizing bacteria was responsible for the attack (Linhardt, 2005).
Corrosion problems in water and wastewater pipelines (steel and iron base) can be mitigated by applying different coatings (Guan, 2001). Several works have been done on the electrochemical behavior of different steel alloys in synthetic wastewater, and the performance of materials was evaluated (Jabalera et al., 2006a; Jabalera, 2006b). In one of the studies, Jabalera et al. (2006a) observed the 1018 steel’s maximum corrosion rate, followed by 410 alloys and 800 alloys. Another work (Jabalera, 2006b) found a minimum corrosion resistance for AISI 1018 and maximum for AISI 800. Microbial influenced corrosion (MIC) of mild steel in dairy effluent was studied, and pit initiation was observed, which is correlated with the presence of microbes Pseudomonas sp., Streptococcus sp., Micrococcus sp., Bacillus sp., Neisseria sp., and Lactobacillus sp. (Babu et al., 2006). Another report highlighted that mild steel corrosion was found to be high enough to require continuous maintenance and early replacement of plant equipment. Thus, mild steel was replaced by 304/304L and 316/316L stainless steel in the construction of ETPs (Tuthill & Lamb, 2007).
The influence of marine water velocity on mild steel corrosion was investigated, and results indicated that there is an increase in corrosion rate with a decrease in water velocity (Melchers & Jeffrey, 2004). Melchers (2007) examined the corrosion of steels in the brackish river water, and findings showed that early corrosion depends upon the dissolved oxygen content but long-term corrosion was a direct function of nitrogenous nutrients pollution, which could be observed due to sewage and surface drainage. Another study on sea water corrosion of steel structure was conducted and followed by linear correlation model (Melchers, 2014). Zhang et al. (2008) investigated new techniques for hydrogen sulfide emission control in sewer systems using microbial fuel cell and inhibitors, e.g. MgO2/CaO2, and formaldehyde was also tested (Zhang et al., 2008). Pretreated coking wastewater was studied for its potential to corrode in cooling water system, and higher corrosion was observed because of the high content of total dissolved solid (TDS), chloride, chemical oxygen demand (COD), sulfide, and oil (Huanzhen et al., 2008). Severe corrosion of metallic equipment such as sludge scrapers, gratings, ladders, and electrical junction boxes was observed in a wastewater treatment plant due to high humidity and hydrogen sulfide (H2S) (Stephenson & Kumar, 2009). Zinc acrylate as anticorrosion agent was studied in activated sludge basins of the effluent from petrochemical plant (Kahn et al., 2009). Steel metal corrosion was studied during the upflow anaerobic sludge blanket treatment of dairy effluent, and a strong connection was correlated with anaerobic treatment and efficiency of COD and phosphorus removal (Jędrzejewska-Cicińska and Krzemieniewski, 2010). Carbon steel corrosion was investigated in untreated and treated effluents from the paint industry, and untreated effluent was observed to be more corrosive due to acidic pH and other chemical constituents (Sasikala & Babu, 2010). Motamedi et al. (2011) studied biocorrosion in wastewater pipelines at a copper mine, and the existing water sample was analyzed for sulfur corrosive bacteria (Motamedi et al., 2011). Another report investigated microbial corrosion on mild steel in cassava mill wastewater, and the microbes identified are Pseudomonas sp., Micrococcus sp., Streptococcus sp., Bacillus sp., Lactobacillus sp., and Neisseria sp. (Akpofure, 2012).
Problems related with paper mill white water corrosivity have been investigated on stainless steel 304L. Cyclic polarization curves indicated that acidic pH, elevated chloride, and thiosulfate increase pitting while sulfate inhibits corrosion (Wang & Singh, 2012). Another report (Singh et al., 2004) showed the stress corrosion cracking and corrosion fatigue behavior of duplex stainless steel in white water, and crack initiation was observed during paper machine shutdowns where ionic concentrations increased. Paper machine environmental conditions such as the amount of dissolved solids (SO4−2 and Cl−), high temperature, and increased biological activity influence the pitting corrosion of stainless steels (Mueller & Muhonen, 1972; Bowers, 1979). Another work (Ram et al., 2012, 2014b) related to paper mill effluent showed that the corrosion in mill effluent was observed to increase at acidic pH, high Cl− content, and chlorophenols, while the addition of SO4−2 tended to inhibit corrosion. Another report (Ram et al., 2015b) on secondary-stage mill effluent showed that anions, viz. SO4−2, PO4−3, NO2−, and NO3−, impart inhibition, whereas Cl− and chlorophenols enhance the corrosion of mill effluent. Mild steel exhibited maximum corrosion, while duplex 2205 showed the lowest corrosion among the tested stainless steels in paper mill effluent.
Several corrosion failures in wastewater treatment facilities were investigated by metallurgical engineering; chemical characteristics and types of corrosion analyzed were pitting, atmospheric, hydrogen sulfide attack, microbial corrosion, etc. (Zamanzadeh et al., 1989). Stainless steel 316L, duplex, and high nickel alloys were tested in synthetic waste solutions of nuclear power plant, and results showed a severe attack on SS 316L; uniform and shallow attack on duplex and crevices on high-nickel alloys were observed (Saito et al., 1989). Corrosivity of treated municipal wastewaters was reported on mild steel, copper, and cupronickel alloys for reuse in cooling water system (Hsieh et al., 2010; Li et al., 2011; Choudhury et al., 2012). The important corrosion-influencing parameters, i.e. ammonia, organic matter, and pH, were identified, and the role of inhibitors was tested. Lou and Singh (2010) investigated the corrosion and pitting on carbon steel in simulating fuel-grade ethanol. Electrochemical tests indicated that increase in water content induces pitting, chloride and acidity promote pit initiation, whereas alkaline condition inhibits corrosion. The corrosion behavior of mild steel was studied in cement and lime slurry having different concentrations of fluoride ions, and it was observed that a low content of fluoride has deleterious action whereas a higher content has inhibitive effect on corrosion (Ghosh et al., 2003).
Authors (Singh & Ram, 2017) worked on the corrosivity of untreated distillery effluent based on the electrochemical polarization tests performed, and results showed that pH, chloride, phosphate, calcium, nitrate, and nitrite in distillery effluent enhanced corrosion, whereas the presence of potassium and sulfate inhibited corrosion. Another research related to corrosion testing on anaerobic treated distillery effluent and electrochemical tests was performed in synthetic solutions, which indicated that Cl− and K+ increase whereas SO4−2, PO4−3, NO3−, and NO2− decrease the corrosivity of effluent at alkaline pH (Ram et al., 2014a). The presence of amino acids (organic matter) and melanoidins (color-imparting chemical) was observed to decrease the corrosivity in distillery effluent. Another work related to in-plant testing on distillery ETP also supports these findings (Ram et al., 2015a).
4 Factors influencing effluent corrosivity
Water pollution not only is harmful to life on earth but also affects the metallic materials used in the construction of ETPs. The nature and concentration of pollutants present in effluent affect the type and rate of corrosion (Nemerow, 1987). Generally, the most important parameters affecting corrosivity of industrial effluents in ETPs are pH, chloride, sulfate, TDS, organic matter, aeration, phosphates, nitrates, temperature, and microbial activity. Table 1 shows the various factors influencing corrosion. The effects of these important parameters are discussed individually below.
4.1 Chemical factors
4.1.1 pH Level
The pH level affects the formation or solubility of protective films. At low pH (<4.5), carbon steel corrodes uniformly, while at higher pH (>9), iron is usually protected (Dave et al., 2004; Paul, 2012). Wastewaters with pH values below 4 are aggressive and promote higher corrosion rates in steel, and austenitic stainless steels provide high chlorides, or other aggressive ions are present (Nixon & Bennett, 2006). Another study investigated the reduction behavior of 1,2,4-triazole and benzotriazole by electrochemical test with varying pH, and the result showed that these compounds are more electrochemically active at acidic pH (Lokesh et al., 2010). In another report (Banenerjee et al., 2012), immersion and electrochemical tests were conducted on mild steel in acidic media with natural grade green polysaccharide as inhibitor and results showed that inhibition efficiency was found to increase with increasing inhibitor. Distillery effluent has shown high corrosivity due to its acidic nature and has affected the materials used in the construction and transport of the effluent. This was further confirmed by the electrochemical tests performed in the distillery effluent and simulated effluent prepared in a laboratory (Ram et al., 2014a; Ram et al., 2015a; Singh & Ram, 2017). Another research cites the role of pH in increasing the corrosivity of paper mill effluent by anodic polarization tests (Ram et al., 2014b).
4.1.2 Chlorides
The effect of chloride ions on stainless steels is very well documented, which affects the activity of passive film on steel surface. This is due to the small size and negative charge of the chloride ion that penetrates through the passive layer to the positively charged metal cation, thus breaking the protective character of passive film (Roberge, 2000; Ibrahim et al., 2009). Stainless steel suffers severe corrosion in chloride-containing environment, where pitting corrosion and stress corrosion cracking take place (Nosier, 2003). Pitting corrosion was observed on stainless steels (AISI 304, AISI 316) in wastewater treatment plants and correlated with chloride ions (Iversen, 2001a). In our previous studies, chloride and chlorophenolic compounds have been found to be corrosion-enhancing chemicals in the paper mill effluent (Ram et al., 2014b). Another work (Ram et al., 2015b) cites the evidence related to pitting corrosion on stainless steels due to chloride in the distillery effluent. Localized corrosion of stainless steels is generally limited to collection system piping (types 304L or 316L) and also occurs in clarifier components depending on the chloride content (Stephen & Bernard, 2006). A previous research commonly agreed that chloride ions cause severe pitting on steels depending on the concentration (Cragnolino, 1983; Hakkarainen, 1998). In another observation, corrosion was found to increase with the increase in chloride concentration, whereas the presence of acid along with Cl− ions enhanced corrosion (Mahato & Singh, 2011). Another work showed the pitting corrosion behavior of steels in chloride-contaminated concrete pore solution by electrochemical test (Singh & Singh, 2012).
4.1.3 Sulfate
Sulfate acts as an inhibitor for the initiation of pits on 304L stainless steel (Wang & Singh, 2012), and the addition of sulfates in chloride-containing solution decreases the pit initiation site and current density (Pistorius & Burstein, 1992). Another report found that sulfate addition mitigates the detrimental effect of chloride ions on pitting potentials of AISI 310 and AISI 316 stainless steels (Bowers, 1979). However, sulfate in wastewater provides nutrition for sulfate-reducing bacteria and contributes to the corrosion of metal components. Sulfates are metabolized under anaerobic conditions in wastewater piping to produce dissolved sulfides, eventually forming H2S (Stephen & Brenard, 2006). The effects of these bacteria are further discussed in section 4.2.
4.1.4 Differential aeration
This influence on corrosion in wastewater, e.g. aggressive cells, is established between the rake arm surfaces within the sludge layer and sludge free surface. The surface above the sludge oxygen concentration is higher, and below the sludge, the concentration of oxygen is lower. Thus, under the sludge, the steel is anodic, while the sludge-free surface is cathodic and creates the corroding cell pair (Munro, 1980).
4.1.5 Natural color and organic matter
The presence of naturally occurring organic color may increase or decrease corrosion, depending on the nature of chemical compounds. However, a study related to the textile industry used a number of dyes such as methylene blue, indigo blue, and crystal violet molecules, and these were found to be inhibitors for iron corrosion in acidic media (Oguike et al., 2013). Other studies (Ram et al., 2015b; Singh & Ram, 2017) related to distillery effluents highlighted the decreasing effect on corrosivity due to melanoidins (color-producing compounds).
The presence of some natural organics can react with the metal surface and provide a protective film and thus reduce corrosion (Sontheimer et al., 1981; Johansson, 1989). Natural organic matter is mostly composed of relatively non-degradable organics, and the possible reasons include the fact that it has been found to encourage a more protective scale, thus reducing corrosion on pipes under some circumstances (Campbell & Turner, 1983; Johansson, 1989). In one observation, mild steel corrosion was found to be reduced due to the formation of iron-organic matter complexes on the metal surface in sea water (Bhosle & Wagh, 1992). The inhibitive action of organic matter in municipal wastewater was also suggested in previous reports (Hsieh et al., 2010; Choudhury et al., 2012). Our previous research (Ram et al., 2014a; Singh & Ram, 2017) compared the corrosivity of distillery and synthetically prepared effluents, which indicated the former to be less corrosive. This may be due to the presence of an organic matter (amino acids) and color, which have decreasing effect on corrosivity. However, not much effort has been reported towards the influence of an organic matter on corrosion, and more work is needed to investigate in this direction. In some cases, organics may provide food to organisms growing in the distribution system. These bacteria can increase iron corrosion through the following pathways (Edwards, 2004): adsorption of nutrients and oxygen resulting in the formation of differential aeration and concentration cells (McNeill & Edwards, 2001), liberation of corrosive metabolites (e.g. ammonia, organic acids, CO2, and H2S) (Parker, 1999), and generation of sulfuric acid from more reduced sulfur compounds (AWWA, 1999).
4.1.6 Total dissolved solids
Higher TDS indicates a high ion concentration in water, which increases conductivity. Higher conductivity has the ability to increase water availability to complete the electrochemical circuit and, further, to conduct corrosive current. The dissolved solids may affect the formation of protective films (Ibrahim, 2005). In one study, permeate from reverse osmosis was observed to be more corrosive than water from thermal distillation due to its high dissolved salts level (Malik & Andijani, 2005). Electrochemical investigations on stainless steel 304 have been conducted in ground water containing high TDS. The various inhibitors were tested for their inhibition efficiency in ground water medium (Gopi et al., 2007, 2009, 2013).
4.1.7 Temperature
Temperature effects are complex, and they also depend on the water chemistry and type of construction material used in the system. In general, the rate of corrosion reactions increases with increased temperature. Temperature in paper mill wastewater systems is typically in the range of 25°C to 45°C and is not a significant factor to increase corrosion (Stephen & Bernard, 2006). However, stress-corrosion cracking of austenitic stainless steels occurs with high chloride and effluent temperature above 60°C (Nixon & Bennett, 2006). Cyclic polarization tests were conducted on steels in simulated environment to understand the mechanism of corrosion in different climatic conditions (Singh et al., 2008). Temperature increase rapidly increases the corrosion current density of stainless steels in the absence of an inhibitor, whereas an opposite behavior has been reported in the presence of corrosion inhibitor (Satpati & Ravindran, 2008). A distillery effluent generated has high temperature around 90°C and heavily affects materials for the construction of ETP.
4.2 Microbial corrosion
Microbial activity due to aerobic and anaerobic bacteria can cause the corrosion of steels. MIC can occur in almost all industries such as oil and gas, power generation, marine, and wastewater systems (Javaherdashti, 1999). Many studies have been performed so far on the MIC on various steels in industrial effluents (Perego et al., 1997a; Iversen, 2001a; Babu et al., 2006; Akpofure, 2012). One investigated the Thiobacillus species involved in the production of sulfuric acid in sewer systems, which caused corrosion (Basic Corrosion Coating Manual, 2011). Thiobacillus bacteria can metabolize sulfur compounds producing an acidic chemical, which leads to the corrosion of steel or iron in wastewater systems (Kelly & Harrison, 1989). SRB has been reported to be involved in the corrosion of carbon steel wastewater piping in the collection system from pulp mill (Stephen & Bernard, 2006). A similar mechanism occurs in carbon steel and stainless steel return activated sludge (RAS) piping systems and in final wastewater piping where biofilm deposits develop and create an anaerobic environment (Munro, 1980). The details related to microbial corrosion in wastewater involvement are shown in Table 2.
Thus, one observes that among the various corrosion prone industries, not much work has been reported in the case of ETPs of the paper mill and distillery industries. In the case of paper mill ETP, corrosion problems occur due to oxygen driven pitting of carbon steel, microbial corrosion of carbon steel and stainless steels, and abrasion enhanced corrosion of grit chamber (Nixon & Bennett, 2006). Another report (Dave et al., 2004)) showed corrosion on carbon steel, stainless steel piping, and agitator shafts, which were correlated with SRB and sulfur oxidizing bacteria (SOB) in paper mill. In the case of corrosion investigations in distillery effluent, mild steel and stainless steels have been tested during distillery spent wash evaporation and with acidic pH, chloride, and other chemical constituents. Results showed better performance for AISI 316 and was thus suggested as a better material for the construction of an incinerator (Thampi & Pandit, 1999). Another study suggested the high concentration of sulfate as one possible factor that results in sulfide corrosion in an anaerobic biodigester in the presence of SRB. Low pH (<4.5), high chloride, and other chemical constituents were also responsible for increased corrosivity (Smuts, 2004). Corrosion-resistant alloys in the form of pipes, tank, and heat exchangers can generate metal ions into the liquor and also limit the useful life of the plant equipment (Wilkie et al., 2000). A recent research (Stanaszek-Tomal & Fiertaka, 2016) showed the biological corrosion of sewers and sewage treatment plants due to the formation of sulfuric acid because of nitrifying bacteria, fungi, and organic acids. Another work (El-Aziz & Sufe, 2013) studied the effect of ammonia and ammonium salts on reinforced steel in sewage treatment systems. The results showed that ammonia has a harmful effect on ordinary Portland cement and sulfate resisting cement mortars, and reinforced steel is greatly affected by the presence of ammonia and aggressive ammonium ions, but high slag cement shows high resistivity. Table 3 presented the chemical and biological factors affecting materials in ETP. The details of the process and ETP of these industries have been discussed in the next sections. Considering the abovementioned facts related to effluent corrosivity, we focused on the effluents from the ETP of paper mill and distillery.
5 Corrosion problem in ETP of industries
There are several water-intensive industries that consume a large quantity of water in their processes and generate a huge quantity of chemically contaminated wastewater. Paper mill and distilleries are identified as wastewater-generating industries and affect the materials in treatment plants. Therefore, we discussed in detail the paper mill and distillery effluents and their corrosivity.
5.1 Pulp and paper industry
A typical paper mill consists of four major sections: pulping, bleaching, paper making, and recovery (Thompson et al., 2001). The different nature of effluents is generated from these processes and contains organic matter, color, lignin, carbohydrates, AOX, and organo- chlorine compounds (US EPA, 1995). Pulping results in lignin network degradation and removal of its soluble fractions from the plant tissue, producing unbleached pulp (cellulose, 80–90%; hemicelluloses, 10–15%; and residual lignin, 2.5–4%). The residual lignin is accountable for the unwanted dark color of pulp (Dence & Reeve, 1996). Bleaching is a multistage process that involves the treatment of pulp with a variety of chemicals in series. The first stage is chlorination by chlorine (Cl2) and/or chlorine dioxide (ClO2) to delignify the pulp, followed by an alkaline extraction (E) stage where alkali (NaOH) and oxygen (O2) and/or hydrogen peroxide (H2O2) are used for the removal of alkali soluble lignin (Kringstad & Lindstrom, 1984); Tessier & Savoie, 2000). Indian paper mills are broadly classified into three categories, i.e. large (>100 tonnes per day), medium (30–100 tonnes per day), and small (<30 tonnes per day) (Subrahmanyam et al., 2001). Large mills (wood and bamboo based) use chemical recovery, while the smaller ones (agro based) with no chemical recovery are extremely polluting (Semwal, 2004).
5.1.1 Paper mill effluent characteristics
The paper industry is considered as the most polluting industry in the world due to its huge quantity and the quality of the effluents generated (Thompson et al., 2001; Sumathi & Hung, 2006). Wood preparation, pulping, pulp washing, bleaching, paper making, and coating operations are the major causes of pollution. The effluents from bleach plant are responsible for most of the chloride, sulfate, TDS, TSS, color, organic matter, and toxicity (Mahadevan et al., 1986; Sumathi & Hung, 2006; Kansal et al., 2008). Bleach plant discharges account for about 60–70% of biochemical oxygen demand (BOD) and 80–90% of color load of the entire mill having chemical recovery (Rao, 1997). The paper-making section requires a large amount of fresh water and produces enormous quantities of wastewater. The quantity and characteristics of mill effluent depend upon the scale of operation, the raw materials used, and the process employed. About 300 m3 of wastewater is generated per tonne of pulp manufactured (Garg et al., 2004). The composition (Table 4) of paper mill effluent includes high COD, BOD, suspended solids, chloride, sulfate, adsorbable organic halides (AOX), color, toxicity, cellulosic compounds, phenols, mercaptans, chlorinated compounds, and high concentration of nutrients (phosphorus and nitrogen) (Pokhrel & Viraraghavan, 2004).
5.1.2 Effluent treatment plant
The effluent treatment process in most pulp and paper mills consists of primary and secondary treatment stages. The mill effluent streams are acidic and alkaline in nature and require a neutralization tank. The primary clarifier provides quiescent flow conditions and removes substantial quantities of a suspended matter, COD and BOD. Most primary clarifiers in mills are circular concrete tanks with sloped bottom, while other parts including rake-mechanism, scraping equipment, piping, pump valve are made of stainless steel 316. Secondary treatment systems use microorganisms to transform and breakdown the organic matter in wastewater, thus reducing the quantities of oxygen consuming substances and chemical that are discharged into the environment. This process is largely focused on BOD reduction and removal. Agitators and pure oxygen reactors are used to keep the wastewater well mixed with bacteria and aerated. The overflow from aeration tanks or chambers goes to the secondary clarifier. Here, suspended solids created by the bacterial action are settled out and removed as sludge. The concentration of bacteria in aeration reactor is maintained by the continuous return of settled biological floc from secondary clarifiers (Stephen & Bernard, 2006).
Corrosion mechanisms affect the performance of various components of the treatment plant. Corrosion problems are typically more severe in the bleached plant than paper mill effluent. These problems are also present in effluents from kraft pulping, sulfite pulping, and thermomechanical pulping (TMP). Pulping and bleaching process streams are normally more corrosive than in the paper-making section (Stephen & Bernard, 2006). However, corrosion problems encountered in treatment plants include oxygen driven pitting of carbon steel, microbial corrosion of carbon and austenitic stainless steels, and abrasion-increased corrosion of grit chamber and allied equipment. Chloride ion concentration above 200 ppm is usually observed in paper mill wastewater and causes localized corrosion of stainless steels (Nixon & Bennett, 2006). Corrosion rates are often greater at the center well in clarifiers where DO levels are higher and at rake arm tips where velocities are higher. Experience has also shown that with lower pH wastewater (as in sulfite pulp mills), the corrosion rates of immersed carbon steel components are greater than in more neutral TMP or neutralized kraft pulp mill effluents. Galvanic corrosion of immersed carbon steel can occur in areas exposed by local failure of coatings, which acts as anode. SRBs flourish in local anaerobic conditions under a slim layer and reduces sulfate to produce hydrogen sulfide, which, in turn, is metabolized by sulfide-oxidizing bacteria (Thiobacillus sp.), thus producing sulfuric acid (Nixon & Bennett, 2006). Thus, the biologically formed acid is present in municipal sewerage systems and corrodes concrete and steel under biofilm deposits. This kind of problem has also been identified in stainless steel waste activated sludge piping, wastewater collection piping, covered tanks, pure oxygen reactor, and stainless steel agitator shafts in pure oxygen reactors (Dave et al., 2004)).
5.2 Distillery industry
Most of the distillery industries in India, China, Korea, Thailand, Poland, and Brazil use molasses, which are by-products from sugar mills (Pant & Adholeya, 2007; Sohsalam & Sirianuntapiboon, 2008; Krzywonos et al., 2009; Sun et al., 2013). Thus, a large number of distilleries are integrated with sugar mills. Distillery is listed as one of the highly water-polluting industries, as noted by the Ministry of Environment, among 17 categories of highly polluting industries. Sugar industries generate molasses as waste, which is used as raw material for the alcohol production by the distilleries (Nandy et al., 2002). Distillery generates an average of 15 L of wastewater (spent wash) per liter of alcohol produced from molasses (Ruiz et al., 2006). Distillery effluent is one of the most complicated wastes to handle due to its acidic pH, high temperature, dark brown color, high ash content, chloride, sulfate, nutrient, and high percentage of dissolved inorganic and organic matter (Aiorella et al., 1983; Beltran et al., 2001). The manufacturing process in distillery involves the main steps of raw material preparation, fermentation, and distillation (Kanimozhi & Vasudevan, 2010). The raw material preparation in alcohol processing involves the dilution of molasses with water to obtain a feed with water to obtain a feed containing 15–16% sugar, and pH adjustment is done with sulfuric acid. The fermentation process involves the diluted molasses solution inoculation with typically 10% by volume of yeast in a fermentation tank (Kanimozhi & Vasudevan, 2010). The mixture is then allowed to ferment anaerobically under controlled pH and temperature. Once the fermentation process is over, settling separates the yeast, and the cell-free broth is taken for distillation (Dias et al., 2010; Kanimozhi & Vasudevan, 2010). The distillation process leads to heat treatment to about 90°C of cell-free fermented broth and further sent to the de-gasifying section of the analyzer column. The distillation process results in the release of a huge quantity of effluent, which has strong environmental impacts (Beltran et al., 2001). The schematics of the manufacturing process of alcohol in distillery is shown in Figure 2.
5.2.1 Distillery effluent characteristics
The volume of effluent from distilleries is approximately 10 times that of the ethanol produced. Distillery effluent is a high-strength waste, and many attempts have been made all over the world to handle effluent. Thus, the effluent requires a systematic treatment to meet the legal requirements before disposal into water resources. The distillery effluent is a high-strength organic effluent, i.e. pH, BOD, COD, phosphate, total solids, TDS, TSS, ammonia, sulfate, color, etc. The effluent has also been proposed for use as a fertilizer, food supplement, biomass production agent, potash source, and animal feed (Pant & Adholeya, 2007)). The range of composition of untreated and anaerobic treated distillery effluents is shown in Table 5.
5.2.2 Effluent treatment plant
Distillery effluent is a bio-recalcitrant waste that is very difficult to treat and is disposed into environment. The effluent causes serious pollution problem, which is generated from alcohol-producing distilleries from sugarcane molasses. The various treatment technologies such as incineration, physico-chemical treatment, composting, biological treatment, and zero discharge of distillery effluent have been studied and evaluated. Anaerobic digestion is a promising technology over aerobic treatment because of low-cost, environment-friendly, and socio-economically acceptability (El-Aziz & Sufe, 2013). Anaerobic treatment converts over half of the effluent COD into biogas (methane and CO2), which further could be utilized for steam production in boilers (Kanimozhi & Vasudevan, 2010). Biocompost has also been prepared after anaerobic treatment, and a filler material (press mud/boiler ash and cane yard waste) has been prepared, dried, and graded. Nowadays, distilleries are going for zero effluent discharge. In most conventional treatment methods, a treated effluent contains high COD, BOD, TDS, TSS, color, and odor, which are being disposed into nearby natural water bodies (Beech & Gaylarde, 1999). Thus, the above fact indicates that the purpose of treatment is based on the belief that the entire organic matter, TSS, color, and odor should be removed before final disposal for the protection of water resources. The present work studied the distillery industry, treating its effluent by anaerobic treatment, evaporation, and final biocomposting.
Metallic equipment such as pipelines, sludge scrappers, storage tanks, heat exchangers, pumps valves, and anaerobic biodigester are used in the ETP of the distillery. Therefore, these pieces of equipment are heavily affected by corrosion due to their acidic nature, inorganic matter, organic matter, chemicals, and high temperature. Distillery effluent is treated anaerobically and has the possibility of MIC in the biodigester and gas collection system (Smuts, 2004). As indicated above, not much work has been reported on corrosion on ETPs of the distillery. The fact that distilleries often use the processing equipment made of corrosion-resistant alloys, especially for acid hydrolysis, in order to resist high temperatures and acidic conditions, is an indication of increased degree of corrosion in this industry. Therefore, corrosion of pipes, tank, and heat exchangers may leak metal ions into the effluent and also limits the useful life of the plant machinery (Wilkie et al., 2000).
6 Conclusion
This study investigates the corrosivity and corrosion-causing factors in industrial effluents, especially from paper mill and distillery. Various studies referred to in this report showed that chemicals and microbes present in the liquor affect the material performance of the treatment plant, thereby reducing the life of plant machinery. In paper mill effluent, the corrosion-enhancing factors identified are acidic pH, chloride, and chlorophenols, while sulfate, phosphate, nitrate, and nitrites act as corrosion inhibitors in effluent. An in depth study of the distillery effluent reveals that chloride, phosphate, calcium, nitrate, and nitrite play a significant role in increasing corrosivity, whereas sulfate, potassium, organic matter (amino acids), and color (melanoidins) inhibit the corrosion at acidic pH. Based on a comprehensive study of literature, the report concludes that duplex stainless steel 2205 has the maximum corrosion resistance, followed by 316L, with 304L with mild steel having the minimum corrosion resistance.
Chemical factors influencing corrosion.
| Sample no. | Factor | Effect |
|---|---|---|
| 1. | pH | Low pH may increases corrosion rate, high pH may protect pipes and decreases corrosion rate |
| 2. | Alkalinity | May help to form protective CaCO3 coating, helps control pH changes, and reduces corrosion |
| 3. | DO | Increases rate of several corrosion reactions |
| 4. | TDS | Higher TDS increases conductivity, and it again increases corrosion rate |
| 5. | Hardness (Ca and Mg) | Ca may form a layer of CaCO3 on metal surface, hence provide protection and reduce corrosion rate |
| 6. | Chloride | Cl− increases the corrosion of iron, stainless steel, copper, and galvanized steel |
| 7. | Sulfate | Sulfate inhibits localized corrosion of stainless steels but may increase corrosion in the presence of SRB |
| 8. | Hydrogen sulfide | Increases corrosion rate |
| 9. | Silicate, phosphate | May form protective films |
| 10. | Natural colour, Organic matter | May increase or decrease corrosion |
-
Source: Environmental Science and Engineering, Inc., 1982.
Microorganisms responsible for microbial influenced corrosion in wastewater.
| Bacterial species | Metal affected | Bio-activity | References |
|---|---|---|---|
| Aerobic bacteria | |||
| Thiobacillus thiooxidans | Iron and steel copper alloys | Oxidizes sulfur and sulfides to form sulfuric acid; damages protective coatings; attacks concrete in sewers | Stanaszek-Tomal & Fiertaka, 2016 |
| Thiobacillus ferrooxidans | Iron and steel | Oxidizes ferrous ions to ferric ions | Bizier, 2007; Stanaszek-Tomal & Fiertaka, 2016 |
| Gallionella sp. | Iron and steel Stainless steels |
Oxidizes ferrous (and manganous) ions to ferric (and manganic); promotes tubercule growth | Basic Corrosion Coating Manual, 2011 |
| Sphaerotilus sp. | Iron and steel Stainless steels |
Oxidizes ferrous (and manganous) ions to ferric (and manganic) Promotes tubercule growth |
Basic Corrosion Coating Manual, 2011; J. Starosvetsky et al., 2008 |
| Sphaerotilus natans | Aluminum alloys Iron and steel Stainless steels |
Some strains can reduce ferric ions to ferrous ions | Basic Corrosion Coating Manual, 2011 |
| Pseudomonas aeruginosa | Corten steel and Carbon steel Stainless steel |
Some strain can reduce ferric ions to ferrous ions | Mansouri et al., 2014; Kurissery et al., 2004 |
| Bacillus sp. | Stainless steel | Some strains can reduce ferric ions to ferrous ions | Kurissery et al., 2004 |
| Gordonia sp. Enterobacter sp. |
Carbon steel | Ashassi-Sorkhabi et al., 2012 | |
| Leptothrix sp. | Iron and manganese | Oxidizes ferrous to ferric ions | Beech, 1999 |
| Anaerobic bacteria | |||
| Desulfovibrio Best known: Desulfovibrio desulfuricans |
Iron and steel Stainless steels Aluminum, zinc, copper alloys |
Utilize hydrogen in reducing sulfate ions to sulfide ions and hydrogen sulfide; promote formation of sulfide films | Kurissery et al., 2004 |
| Desulfotomaculum Best known: D. nigrificans |
Iron and steel Stainless steels |
Reduce sulfate ions to sulfide and hydrogen sulfide (spore formers) | Basic Corrosion Coating Manual, 2011 |
| Desulfomonas sp. | Iron and steel | Reduce sulfate ions to sulfide and hydrogen sulfide | Basic Corrosion Coating Manual, 2011 |
Chemical and microbial influenced corrosion problems in ETP.
| Sample no. | Application/system | Problem components/areas | Microorganisms |
|---|---|---|---|
| 1. | Pipelines/storage tanks (water, wastewater, gas, oil) | – Stagnant areas in the interior – Exterior of buried pipelines and tanks, especially in wet clay environments |
– Aerobic and anaerobic acid producers – Sulfate reducing bacteria Iron/manganese oxidizing bacteria – Sulfur oxidizing bacteria |
| 2. | Cooling systems | – Cooling towers – Heat exchangers – Storage tanks |
– Aerobic and anaerobic bacteria – Metal oxidizing bacteria – Slime forming bacteria – Algae – Fungi |
| 3. | Piers, docks, and other aquatic structures | – Splash zone – Just below low tide |
– Sulfate reducing bacteria |
| 4. | Power generation plants | – Heat exchangers – Condensers |
– Aerobic and anaerobic bacteria – Sulfate reducing bacteria – Metal oxidizing bacteria |
| 5. | Fire sprinkler system | – Stagnant areas | – Sulfate reducing bacteria |
Characteristics of the pulp and paper mill effluent.
| Parameters |
References | |||||||
|---|---|---|---|---|---|---|---|---|
| pH | TDS | TSS | COD | BOD | Cl− | SO4−- | Colour | |
| 9.8±0.0 | ND | ND | 1303±25 | 148±5 | ND | 677±7 | ND | Rodrigues et al., 2008 |
| 8.0–9.0 | 1484–1935 | ND | 370–950 | 142–354 | ND | ND | 1321–2443 | Singh et al., 2011 |
| 11.45±0.2 | 5.5±0.4 | 170±7 | 160,810±919 | ND | ND | ND | Dark brown | Herath et al., 2011 |
| 7±0.5 | 6000±50 | ND | 2900±90 | ND | ND | ND | ND | Razali et al., 2012 |
| 6.6–10 | ND | 620–1120 | 646–1433 | 240–380 | ND | ND | 2212–5830 | Choudhary et al., 2011 |
| 7.0 | ND | 70 | 850 | ND | 85 | 150 | Dark brown | Gönder et al., 2011 |
| 7.8±0.4 | ND | 344±261 | 2319±618 | 959±394 | ND | 496 ± 110 | Dark brown | Merayo et al., 2013 |
| 7.78 | 2380±9 | 112±6 | 692±11 | 128±16 | 500±25 | 172±18 | 1107±14 | Ram et al., 2014b |
-
ND, not detected. All values in ppm except pH, color (pt-co units).
Schematics of alcohol manufacturing and effluent generation.
Typical characteristics of untreated and treated distillery effluent.
| Parameters |
References | |||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| pH | TS | TSS | TDS | COD | BOD | Total N | Potassium | Phosphate | Cl− | SO4−- | Colour | |
| Distillery untreated effluent | ||||||||||||
| 4.16±0.03 | 87,855±200 | 6855±120 | 81,000±150 | 11,000±180 | 47,100±250 | 355±30 | 12,100±30 | 250±15 | 5500±60 | 5050±90 | Dark brown | Singh & Ram, 2017 |
| 3.0–4.5 | 110,000–190,000 | 13,000–15,000 | 90,000–150,000 | 110,000–190,000 | 50,000–60,000 | 5000–7000 | ND | 2500–2700 | 8000–8500 | 7500–9000 | Dark brown | Mohana et al., 2009 |
| 5.5 | 18,336 | ND | ND | 49,105 | 22,418 | 35.4 | 270 | 35.4 | ND | ND | ND | Bustamante et al., 2005 |
| 3.0–4.1 | 51,500–100,000 | ND | ND | 100,000–120,000 | 30,000–60,000 | 1800 | 180 | 139 | ND | ND | ND | Melamane et al., 2007 |
| 4.4–4.6 | ND | ND | ND | 45,000 | 198,000 | 710 | 3817 | 87 | ND | 3730 | ND | Costa et al., 1986 |
| 3.2–3.6 | ND | ND | ND | 145,000–180,000 | 100,000–140,000 | ND | ND | ND | ND | ND | ND | Beltrán et al., 2001 |
| 3.8 | 32,000 | 3700 | ND | 40,000 | ND | ND | ND | 130 | ND | ND | ND | Borja et al.,1993 |
| 7.1±0.2 | 21,110±970 | 12,300±560 | ND | 29,970±1560 | 14,800±440 | 6630±300 | ND | 1120±60 | ND | ND | ND | Yetilmezsoy et al., 2009 |
| 3.8–4.4 | 60,000–90,000 | 2000–14,000 | 58,000–76,000 | 70,000–98,000 | 45,000–60,000 | 1000–1200 | 5000–12,000 | 500–1500 | 5000–8000 | 2000–5000 | ND | Goyal et al., 1996 |
| Anaerobic treated effluent | ||||||||||||
| 7.5–8.0 | 70,000–75,000 | 38,000–42,000 | 30,000–32,000 | 45,000–52,000 | 8000–10,000 | 4000–4200 | 2000–3000 | 1500–1700 | 7000–9000 | 3000–5000 | Dark brown | Mohana et al., 2009 |
| 7.8 | ND | 12,180 | 28,320 | 34,000 | 6300 | 1754 | 5170 | 157 | 3000 | 7120 | Blackish brown | Chaudhary et al., 2010 |
| 7.44±0.03 | 39,420±200 | 4860±120 | 34,560±80 | 44,500±180 | 7450±200 | 200±15 | 3550±16 | 110±8 | 4500±80 | 4250±100 | Dark brown | Ram et al., 2014a |
-
ND, not detected. All values in ppm except pH.
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Articles in the same Issue
- Frontmatter
- In this issue
- Reviews
- Organic green corrosion inhibitors (OGCIs): a critical review
- Managing corrosion in desalination plants
- Study on corrosion investigations in industrial effluents: a review
- Corrosion and corrosion prevention in heat exchangers
- Lead-silver anode behavior for zinc electrowinning in sulfuric acid solution
- Original article
- Sensitization of an austenitic stainless steel due to the occurrence of δ-ferrite
Articles in the same Issue
- Frontmatter
- In this issue
- Reviews
- Organic green corrosion inhibitors (OGCIs): a critical review
- Managing corrosion in desalination plants
- Study on corrosion investigations in industrial effluents: a review
- Corrosion and corrosion prevention in heat exchangers
- Lead-silver anode behavior for zinc electrowinning in sulfuric acid solution
- Original article
- Sensitization of an austenitic stainless steel due to the occurrence of δ-ferrite
