1.

0 Introduction Spent caustics are the most difficult of all industrial wastes to dispose properly, with the exception of radionuclide wastes. In other words, spent caustic is a waste industrial caustic solution that has become exhausted and is no longer useful (or spent). Since the dawn of petroleum refining, caustic solutions containing sodium hydroxide (common lye) have been used to wash sulfur and other undesirable compounds out of petroleum. Its use has been in washing crude oils, intermediate fractions, and finished fuels throughout the refining processes. The result of this washing is the generation of spent caustics also called Waste Caustics and Toxic Wastes. Another form of sulfur bearing wash solutions from other refining operations is Sour Water. Sour Water contains fewer amounts of sulfur compounds, but is generated in much greater volumes. In addition to the refining industry, other industries including chemical manufacturing, LPG (liquefied petroleum gas), Natural Gas (methane),

and geothermal energy plants produce huge volumes of Sour Water and Spent Caustics. Chemical manufacturing produces spent caustics containing specific compounds compared to the wide variety from refining operations. LPG and Natural Gas plants predominately produce potassium hydroxide spent caustic, whereas, most other sources produce sodium hydroxide spent caustic.

1.1 Constituents of spent caustics In refinery petroleum production, there are many types of waste which can produce different types of spent caustic during process step for the removal of sulphur which can be classified four major constituents that are : i) ii) iii) iv) Extremely contains hydrogen sulfide Highly levels of mercaptans Highly levels of phenol Naphthanics levels

a) Extremely contains hydrogen sulfide

Common to all spent caustics is a high concentration of the extremely deadly and odorous hydrogen sulfide, an acutely toxic gas most recognized as the odor of rotten eggs when in low ppb (parts per billion) concentrations. Hydrogen sulfide gas readily dissolves in caustic solutions due to its solubility at high pH or "caustic pH" conditions, typically above pH 10 to 12. It can be released from solution as a gas easily when the solution is disturbed or the pH is lowered. It is more toxic than hydrogen cyanide to humans and death can occur in exposures of just 100 to 500 ppmv (parts per million by volume) in the atmosphere.

Hydrogen sulfide gas is responsible for "multiple sewer-workers death syndrome". It starts with 1 worker while working in a sewer suddenly collapses, one by one up to 4 more workers rush in to help the collapsed worker then collapse ontop of each other like a dog-pile. By now the 6th worker sees the calamity and decides to get help instead of entering the sewer. Multiple deaths have occurred in cities worldwide since the first wastewater sewers were built. It was believed that sewer deaths were due to a lack of oxygen before the toxicity of hydrogen sulfide was understood. Furthermore, hydrogen sulfide contained in an oxygen

environment can be explosive when ignited, thus adding to the danger.

b) Highly levels of mercaptans

Petroleum, LPG and Natural Gas manufacturing plants may also generate spent caustics containing high levels mercaptans. Naturally occurring mercaptans, also known as organic sulfides or thiols, contain a sulfur atom typically near the end of an organic molecule or chain. Mercaptans are the most odoriferous compounds known to man and even a minuscule amount in ppb concentration (parts-per-billion), is easily detected by the human nose. For example, the odor of Skunk is mostly butyl-mercaptan. Ethyl-mercaptan is intentionally fed into natural gas pipelines in ppb levels to serve as an "odorizer". When a person "smells a gas leak" they're not smelling the Natural Gas, instead, they're smelling the mercaptan odorizer since LPG and Natural Gas are odorless.

The LPG propellants used in aerosol canned products (after CFC's were banned) must be specially deodorized to prevent the odor of mercaptans being detected by the user. For example, men's aerosol shaving cream is particularly sensitive to discovery if any mercaptans remain in the propellant. Therefore, LPG aerosol propellants are much more expensive than other LPG products.

c) Highly levels of phenol

Refinery spent caustics contain several other compounds in high levels including phenol together with cresylic and naphthenic acids that also exhibit toxic and odorous properties. Phenol is a known biocide used in medicines and for early sanitation in hospitals, etc. For example, the trademark Champo-Phenique stands for camphor and phenol and is sold over-the-counter to treat bacteriological infections. It has been established that when as little as 64 square inches (or an area of 8 inches x 8 inches) of skin is covered with pure phenol death will occur. Other hydroxy-phenols include catechol, resorcinol, and hydroquinone (these compounds, shown with their common names, are also known as hydroxy-benzenes and dihydroxy-benzenes).

d) Naphthanic levels

Refinery naphthenic spent caustics are the last of the major chemical classifications that may contained in relatively high concentrations. Naphthenics generally do not impart a toxic or objectionable odor component to spent caustics. Naphthenics are partially soluble in caustic and increase the total organic carbon (TOC) content considerably. Naphthene is a general term for cyclic alkanes, or cyclic non-aromatic hydrocarbons called cycloalkanes. Refinery naphthenes typically include cyclopentane and cyclohexane as the parent compound. Many refineries don't discriminate too closely and often include the family of naphthenic acids, or cyclic carboxylic acids, when referring to naphthenics in general terms. Naphthenic acids contain a cyclic naphthene parent compound bonded to various hydrocarbon chains containing a carboxylic acid end group. A "catch-all" analytical procedure includes Total Acid Number (TAN) for a rough

value of the naphthenic acid content. Other analytical methods are necessary for concise identification of each naphthenic species.

1.2 Spent caustic treatment by strong oxidation Spent caustic streams from refineries and ethylene production typically have a high chemical oxygen demand (20 - 500 g/L) and contain contaminants that are hazardous, inhibitory and/or bio-refactory. These contaminants can include reduced sulfur compounds such as sulfides and mercaptans, as well as organic species such as the sodium salts of naphthenic and cresylic acids. Due to the types of contaminants contained in spent caustic, these wastewaters can be environmentally hazardous and difficult to treat with conventional biological treatment. Usually, in petroleum industries they used wet air oxidation but new technologies have been developed in order to treats the spent caustics using many types of treatment including strong oxidation. Spent caustic from caustic towers in ethylene plants contains significant contaminants, which include dissolved hydrocarbon, polymers, and active polymer precursors in addition to the well-defined levels of sodium salts and free caustic. These lesser-known contaminants can foul spent-caustic-processing equipment and grossly inhibit the oxidation level of sodium sulfide to sodium sulfate. The polymerization rate of polymer precursors increases with increasing temperature and pressure. Polymerization of the carbonyls by aldol condensation is catalyzed by free sodium hydroxide in solution, while additional polymerization of dienes is catalyzed by oxygen, oxidizing agents, and heavy metal ions. The organic constituent of the spent caustic is present in two forms: a dissolved phase and a free separate phase. The organic components dissolved in the aqueous phase have different concentrations defined by their solubility limits. On the other hand, the unsaturated hydrocarbons and light aromatic components have significantly higher solubility limits than the saturated and heavy organics. The organics present in the spent caustic beyond their solubility limit in the aqueous phase exist as a separate phase in the form of oily droplets and solid polymer particles that are visible within the spent-caustic solution.

Thus, pretreat enhances the oxidation process, resulting in more efficient oxidation (better conversion of Na2S to Na2SO4) and potential elimination of a secondary oxidation step.

2.0 Process of Strong oxidation In oil refining, the spent caustic liquors was from the extraction or treatment of acidic impurities, such as hydrogen sulfide, mercaptans and organic acids in hydrocarbon streams. These spent caustic streams are a significant odour source as well as troublesome to the operation of a bio-treatment facility. In addition, the Chemical Oxygen Demand (COD) in spent caustic is usually very high (10,000 100,000 mg/l), and the contaminants in spent caustic typically include sodium carbonate, sodium sulfides, mercaptans, phenols, and emulsified hydrocarbons Generally, the alkali solution (caustic) has been used widely for treating the petroleum products. Moreover, the odour and colour was discovered can be improved by removing organic acids (naphthenic acid and phenols) and sulphur compounds (mercaptans and hydrogen sulphide) led to the development of caustic washing. The process consists of mixing a lye solution with a petroleum fraction. The treatment is carried after distillation of the petroleum fraction since contract with air forms free sulphur which is very corrosive and difficult to remove. Furthermore, the lye reacts with any hydrogen sulphide present to form sodium sulphide which is soluble in water. Besides that, spent lye is termed as a caustic solution with about 65% of sodium hydroxide has been used by reaction with hydrogen sulphide, light mercaptans, organic acids or mineral acids. But, the caustic solution spent by hydrogen sulphide is not regenerated. Thus, there is availability of numerous processes that can effect more complete removal of contaminating materials:

Figure 2.1: Flow diagram of oxidation treatment unit

2.1 Chemical Oxidation (Hydrogen Peroxide)

In-Situ Chemical Oxidation (ISCO) depends on on the critical capacity of oxidants to chemically destroy the bonds of the hydrocarbons. Complete chemical oxidation of gasoline would produce carbon dioxide and water. Chemical oxidants work by producing free radicals, such as the hydroxyl radical, which oxidize the gasoline.

Figure 2.2: Schematic diagram of In situ chemical oxidation

In this process, spent caustic is mixed with water-immiscible solvent for extraction of polymerized hydrocarbons to avoid fouling in downstream equipment. The residence time is supplied to the mixture to get phase separation and then the solvent phase is removed from the aqueous phase. The aqueous phase is then treated with air for oxidation in a process like WAO to reduce COD. Na2S + 4H2O2 Na2SO4 + 4H2O

Hydrogen peroxide is used in the oxidation of reduced sulphur compounds without producing toxic products. It is cost effective, specific and safe. Most hydrogen peroxide applications involve its simple injection into the water stream with no requirement for additional chemicals or equipment. These include the control of bio-growth, the supply of supplemental oxygen, the removal of chlorine residuals, and the oxidation of sulphides, metals, and other easy-to-oxidize components of BOD/COD. Activation of H2O2 in these applications may be affected by the adjustment/control of pH, temperature, and/or reaction time.

The reaction between sulphides and hydrogen peroxide depend on pH of solution. The use of hydrogen peroxide is efficient when the sulfide exists as molecular hydrogen sulphide (H2S) react on 1:1 (w/w) with hydrogen peroxide to form elemental sulfur.

Figure 2.3: pH reaction between sulphides and hydrogen peroxide depend on pH of solution

At alkaline pH (8-9), H2O2 takes four times as much hydrogen peroxide to turn S2- ion into sulfate. The reactions that occur in each pH range are: Acid pH H2S + H2O2 Neutral pH H+ + HS- + H2O2 HS- + 4H2O2 Alkaline pH S2- + 4H2O S + 2H2O

S + H2O SO4 +4H2O +H+

2-

SO42- + 4H2O

2.1.1 Application of Chemical Oxidation Odor control Hydrogen peroxide oxidizes hydrogen sulfide, mercaptans, amines and aldehydes. It may be applied directly to aqueous wastes containing these odorants, or to wet scrubbers used to remove them from airstreams. H2O2 may as an alternative be added as a preventative to eliminate the anoxic conditions which favour the generation of odours if the odours are the consequence of biological activity. Corrosion control Hydrogen peroxide destroys residual chlorine and reduced sulfur compounds thiosulfates, sulfites, and sulphides which form corrosive acids when condensed onto processing equipment and oxidized by air. BOD/COD removal Hydrogen peroxide oxidizes both organic and inorganic pollutants which contribute to BOD and COD whereas catalytic hydrogen peroxide may be desired to oxidize the more resistant substances. Thus, hydrogen peroxide may also affect BOD/COD removal by enhancing the performance of other processes.

2.2 Fenton oxidation

Figure 2.4: Schematic diagram of Fenton oxidation

The Fenton reaction consists of the oxidation of organic molecules by use of hydroxyl radicals (HO-). These arise from the controlled decomposition of hydrogen peroxide in which iron acts as an activator or the hydrogen peroxide. For start-up of the process of Fenton oxidation, phenol spent caustic is pretreated by heating and pH regulation. Once the temperature of the process stream reaches 80C, the first agent starts the process (turn on the pump 2) and starts manipulating the Fentons reagent coming into the buffer tank (pump 3) to learn to handle the oxidation process. After the oxidation process, the water is pump to pH neutralization reactor to adjust the pH to neutral then it is drain out for disposal or reuse purpose. The Fenton process able to remove the dissolved organic carbon (DOC) content of a petroleum refinery spent caustic stream which was previously treated by the Wet Air Oxidation (WAO) process. The oxidation of the organic matter present in the pre-treated spent caustic stream (PTSC) is described based on the Fentons classic reactions.

Fe2+ + H2O2 HO + Fe2+ Fe3+ + H2O2 Fe3+ + HO2 HO2 + H2O2 RH + HO2RH + H2O2 Fe3+ + RCO2-

Fe3+ + HO2- + OHOH- + Fe3+ HO2 + Fe2+ + H+ Fe2+ + O2 + H+ H2O + HO2 oxidation products oxidation products Fe3+(RCO2)2+

In Fenton oxidation, the hydroxyl radical reacts rapidly with most organic compounds by abstraction of carbon bound hydrogen and double bound addition initiating a sequence oxidative degradation reaction which may lead to complete mineralisation of organic contaminants. Fenton's reaction is recommended as a method for reduction of total COD and total phenols in spent caustics. The toxic contaminants such as Malathion, methyl tertbutyl ether (MTBE), phenol and dichlorodiphenyltrichloroethane (DDT) were effectively oxidized in the existence of Fe and H2O2. Almost all of sulfide is supposed to be converted into sulfate within 30 minutes of reaction time. The complete sulfide removal also affected the COD to be reduced and form sulfate. Thus, the Fe-H2O2 system is proper to be applied for treating industrial wastewater for reducing phenolic compounds and COD. The overall COD removal was around 78% and the efficiency is comparable to that of a traditional Wet Air Oxidation (WAO) process of around 75%. An amount of ferrous sulphate and a volume of hydrogen peroxide were selected to start the Oxidation with the Fenton Reagent reaction for DOC Removal. DOC development was checked until it remained constant. Then, hydrogen peroxide was periodically added to the reaction medium, until no additional DOC removal was observed. At this moment, ferrous ions were not available whereas addition alone of

hydrogen peroxide was not able to generate enough hydroxyl radicals. So, ferrous sulphate was added again and peroxide was continuously added to the medium until a new "plateau" was reached. This procedure was repeated many times as far as either the addition of hydrogen peroxide or ferrous sulphate did not result in any additional DOC reduction. Besides that, this method was used to obtain a decrease in total phenols from 5,200 mg/L to less than 130 mg/L. The greatest removal occurred within a pH range of 2.76 with a mass ratio of 1:3 (Fe3+ /H2O2) and over 30 min reaction time. Under these conditions, 99.5% of total phenols and 95.5% of COD were removed while sulphides and mercaptans decreased to <0.1 mg/L.

2.3 Fenton Sludge Recycling (FSR) Process

Fenton process is the use of iron (II) salts as catalyst is certainly the simplest method to produce the HOradical. However there also as a limitation for this process which the iron (III) production which in form of hydroxides/oxides is produced as residual product, the so-called Fenton sludge. This sludge contains adsorbed organic compounds and needs further sludge treatment (dewatering) and disposal at special dumping sites, creating additional costs. To overcome the sludge problem of the Fenton process comprehensive research activities have been initiated which a special process with sludge recycling after an electrochemical reprocessing step (Fenton Sludge Recycling). The patented process meanwhile applied to treat a high loaded effluent from a chemical production plant was first developed and optimized in a pilot plant and afterwards tested on industrial scale.

Figure 2.5: Flowchart of FSR process Chemical production in pilot plant was performed in a reactor to modify oxidation and coagulation process for reducing sludge production from landfill leached treatment. At first, sulphuric acid was added to adjust pH into 5 which is suitable condition for both Fenton oxidation and coagulation process. The maximum COD and colour removals were obtained when H2O2/Fe2+ was added at ratio 1:3:1. The iron also added in the form of a ferrous sulfate solution. Then, Fenton oxidation reaction occurs rapidly after chemical addition. . Followed by, the leachate treated by Fenton oxidation process was passed into the sediment reactor which adjusted into pH 5 by NaOH. Therefore, recycling of Fenton sludge to a coagulation reactor was attempted to reduce the coagulant dose and sludge production.

2.4 Application of strong oxidation methods

Treatment method Chemical oxidation

Sulfidic spent caustic Suitable

Phenolic spent caustic Unsuitable

Naphthenic spent caustic Unsuitable

Mixed spent caustic Potentially suitable depending on bio-system feed limits Unsuitable

Fenton oxidation

Unsuitable

Suitable

Potentially suitable depending on bio-system feed limits

2.5 Advantages and disadvantages of strong oxidation for spent caustic treatment

Technique Chemical oxidation

Operating condition Ambient temperature: Atmospheric pressure: pH:8-9 residence time: < 0.5 hr Ambient temperature: Atmospheric pressure: pH:2-4 Catalyst :Iron Residence time: < 1 hr

Major needs H2O2 injection H2O2 bulk inventory

Advantages Complete oxidation of sulphides Low CAPEX

Disadvantage High peroxide consumption Its availability in proximity may be an issue

Fenton oxidation

H2O2 injection H2O2 bulk inventory FeCl3 injection

Oxidation of organics Low CAPEX

High peroxide consumption Unsuitable for sulphides removal Handing of corrosive sulphuric acid Generates chemical sludge

2.6 Limitations a) Hydrogen Peroxide Due to these properties of spent caustic it is very difficult to control chloride content in the overhead and higher amount of sodium may end up in the residue. i. Never use spent caustic for crude neutralization as it contains higher amount of sodium ii. Has less capacity to neutralize the overhead water.

b) Fenton Oxidation i. The amount of oxidant or hydrogen peroxide required to increase hydroxyl radical is large which increases the cost of operations. ii. The system is able to destroy some inorganic contaminants such as sulfides and mercaptans as well as the process is easy to install and has low capital cost

3.0 New technology of advanced oxidation processes (AOP) Advanced oxidation processes (AOP) are technologies based on the generation of highly reactive species, hydroxyl radicals (OH) which used in oxidative degradation procedures for organic compounds dissolved in water or wastewater. Hydroxyl radical is the second most powerful oxidant due high oxidation potential after fluorine. The difference between types of oxidant is tabulated in the Table 3.1. The hydroxyl radical can be generated from several AOP to give the better efficiency according to specific treatment.

Table 3.1: Standard reduction potentials of some oxidants in volts (V) compared with the normal hydrogen electrode (NHE, E0 = 0 V). Sources: Adapted from Legrini and coworkers (1993)

Oxidant Fluorine (F2) Hydroxyl radical (OH) Ozone (O3) Hydrogen peroxide (H2O2) Potassium permanganate (KMnO4) Chlorine dioxide (ClO2) Chlorine (Cl2) Bromine (Br2)

Standard reduction potential/V 3.03 2.80 2.07 1.77 1.67 1.50 1.36 1.09

3.1

Hydrogen peroxide and ultraviolet radiation (H2O2 / UV) oxidation Hydrogen peroxide (H2O2) is a strong oxidant to reduce the levels of

pollutants present in wastewaters. However the individual H2O2 is not efficient in oxidizing more complex material. With combination of UV irradiation, H2O2 are available to decompose and generate hydroxyl radicals as shown in equation below

H2O2

hv 2HO

This reaction depends on the pH parameter. When the pH is increased the more hyrdroxyl radical is produced due to the increases in amount of hydroxyl.

H2O2 + HO H2O2 + HO2 2HO2

HO2 + H2O HO + O2 + H2O H2O2+ O2

In Philippopoulus and Poulopoulos et al (2003) studied stated the application of the H2O2/UV process to purify oily from wastewater from a lubricant by an oil company it was found that in acid at pH 3.5, there was enhanced reduction in the COD of the waste water compared to neutral and basic pH. Hu and coworkers (2008) also reported that the H2O2/UV was able to remove the up to 98% contaminated underground water due to leakages in gasoline station tanks which cause rises in H2O2 concentration.

3.1.1 Advantages H2O2/UV is higher pollutant removal compared to single UV or H2O2. Reagent H2O is totally soluble in water and it is no need for a separation process after the treatment.

3.2

Ozone and ultraviolet radiation (O3/UV) oxidation The advantages using of ozone is not harmful to the organism. However, there

is limited use on waste water due to the high demand of energy to generate ozone. The efficiency of ozone in degrading the organic compound is improved by combining it with H2O2 and Uv radiation or ultrasound. The O3/UV process consists in UV irradiation (254 nm) on an aqueous system saturated with ozone producing H2O2 as shown by equation below:

O3 + H2O

hv

H2O2 + O2

Hydrogen peroxide is formed, then the ozone will react with hydrogen peroxide to produce hydroxyl radical.

2O3 + H2O2

2OH + 3O2

3.2.1 Advantages O3/ UV system are higher pollutant removal than ozone or UV light and it more hydroxyl radicals.

3.3

Ozonehydrogen peroxideUV radiation (O3/H2O2/UV) oxidation The addition of H2O2 to the O3/UV process speed up the decomposition of

ozone which resulting in an increased rate of number of OH generation. In processes that involving weak absorbers of UV radiation pollutants, it is more cost effective to add hydrogen peroxide externally at a reduced UV fluxes. If direct photolysis of pollutants is not a major factor, O3/H2O2 should be considered as an alternative to photo-oxidation processes. The capital and operating costs for the UV/O3 and/or H2O2 systems vary widely depending on the wastewater flow rate, types and concentrations of contaminants present, and the degree of removal required.

Table 3.2: Comparison of the operating costs of various AO Process O3/UV O3/H2O2 H2O2/UV Photo-catalytic oxidation Cost of oxidant High High Medium Very low Cost of UV Medium 0 High Medium to high

3.4

Fenton and persulfate oxidation with zero-valent iron In recent years, persulfate (S2O82) has received growing attention as a

potentially alternative for the chemical oxidation of organic pollutants. A strong and non-selective oxidant (Eo = 2.01 V), persulfate is relatively stable at room temperature. It can be activated by heat, UV light, or transition metal ions to form sulfate radicals which are persulfate. In a persulfatewater system, hydroxyl radicals (OH, Eo = 2.70 V) can also be formed at alkaline pH, which may participate in contaminant oxidation. The transition metal cations such as Fe2+ have been used to activate persulfate for the oxidation of organic chemicals. Zero-valent iron Fe(0) has been used intensively in water treatment processes because it is passive, inexpensive, and nontoxic. Fe(0) has been applied as a catalyst to activate persulfate for the degradation of toxic compounds. even stronger oxidizing agents (Eo = 2.60 V) than

Fe(0) (s) + S2O82 (aq) Fe2 (aq) + S2O82 (aq)

Fe2 (aq) + 2 S2O82 (aq) Fe3(aq) +SO4- (aq) + SO42- (aq) 3Fe2 (aq)

2Fe3(aq) + Fe(0) (s)

Fe(0) has also been investigated as a source of Fe2+ to catalyze H2O2 in Fenton oxidation. Similar to Equations above Fe(0) can release Fe2+ in the presence of H2O2 to generate hydroxyl radicals like equation below.

Fe(0) (s) + H2O2 (aq) Fe2(aq) + H2O2 (aq)

Fe2 (aq) + 2OH(aq) Fe3(aq) + OH (aq) + OH (aq)

Seok & Dong et al (2012) research investigated the oxidation of spent caustic, strong alkaline liquid waste from refinery and petrochemical plants by hydrogen oxide and persulfate activated with zerovalent iron, Fe(0) as an alternative treatment process.

3.4.1 Advantages Oxidant-activating agent, Fe(0) is more effective and longer-lasting than Fe2+ and potentially more suitable for the oxidation of spent caustic. Fe(0)-activated persulfate can remove approximately 10% more TOC than the Fe(0)H2O2 system. Persulfate is better for oxidizing spent caustic than H2O2 in the presence of Fe(0).

4.0 Conclusion Mixed refinery spent caustic is an industrial wastewater that is generated from oil refineries. Spent caustic undergo two treatment steps: chemical oxidation followed by biological post treatment step. The goal of chemical oxidation is to drop the contamination concentration to a level that biological treatment can take place. The maximum contaminants concentration, which can be measured by chemical oxygen demand, that biological treatment can be applied, is 1,000 ppm. Advanced oxidation processes, in specific, Fentons reaction is tested to check if the method can be applied to spent caustic treatment. The basic concept of wastewater treatment can be simply put as the conversion of contaminants characterized as chemical oxygen demand (COD) into substances of non-COD via application of an oxidizing agent, such as oxygen gas. Ideally, carbon dioxide (CO2) and water (H2O) would be the desirable final products in waste treatment; yet, many incompletely oxidized compounds or compounds resistant to oxidative reaction remain in the water solution. Those compounds, categorized as low oxygen demand substances, are the most difficult to remove from water being treated.

Oxidative methods used in the field of wastewater treating include: 1. Application of strong oxidizing agents, such as permanganate, chromate, ozone, hydrogen peroxide activated by UV or hydro-oxy radical, etc., to chemically oxidize contaminants in water. 2. Organic compounds are decomposed or assimilated into bacterial cells at the expense of oxygen in maintaining the biological cell activities.

3. Organic contaminants are destroyed by rapid oxidation through high temperature gasification/combustion, i.e., incineration. The spent caustic generated in ethylene plants can be used in pulp and paper mills as makeup alkali in the Kraft recovery process. The hazardous nature of aromatic hydrocarbons, polymers, and polymer precursors, however, tends to inhibit this practice. By reducing the quantity of hydrocarbons, polymers, and polymer precursors to less than 10 ppm in the spent caustic, the Pretreat process makes spent caustic attractive for use in pulp and paper mills. Pretreat converts a hazardous waste in the ethylene plants to a valuable byproduct. Other similar uses of pretreated spent caustic are found in noble metal catalyst manufacture, metal treatment processes, and leather tanning. The large number of pulp and paper units throughout the world (5,700 totals) offer under-utilized opportunities for economic and environmentally responsible disposal of spent caustic from the ethylene unit.

5.0 RECOMMENDATION FOR IMPROVEMENT a) Corrosion control (Hydrogen Peroxide) After a detailed review of the caustic injection system, recommendations were given at the end to improve the system performance in order to get better corrosion control and to decrease sodium content in the residue. It is fine to use spent or fresh caustic for the crude overhead neutralization. The caustic is injected in small amount and it is much diluted. The caustic is injected directly to the desalted crude. It is recommended that the diluted caustic should be premixed with a slipstream of the desalted crude, typically 1 wt% of crude, before it is added to the desalted crude line to achieve better mixing. The premixing of caustic with desalted crude will help increase the injected volume and enhance mixing. There is also advantage of limiting the contact of caustic with the feed pipelines. Not only that, there is no mud wash system installed in the desalters. Accumulation of dirt particles at the bottom of the desalter will gradually occur with the course of time. Under deposit corrosion may be observed under this accumulated dirt which could result in decrease in efficiency of the desalter operation. The installation of a mud wash system in the desalters was recommended by Jelle Bouma. It was recommended to change the chloride specification in the overhead water from currently 3 ppm to 5-10 ppm. To achieve the low chloride specification of 3 ppm more caustic has to be injected and as a result there will be an increased risk of the sodium in the residue becoming off spec. To avoid the corrosion on the shell side in the preheat train in the DHT due to entrained water containing ammonia and chloride a coalesce should be installed before the DHT feed pump. It is important to monitor the level of the emulsion layer because a higher layer will result in shut down of electricity between the electrodes and carry-over of emulsion to the crude tower as a result. This carry-over will give rise to fouling in downstream equipment and corrosion control will be affected.

Besides, spent caustic injection to crude to overcome corrosion in the overhead is considered a good solution for waste reduction in refineries. Although sulphidic spent caustic usage for corrosion control is considered a good way for reduction of waste and is recommend by many experts, most companies do not reuse

their spent caustic. Reuse of spent caustic for corrosion control can only be done in a very controlled way. It is much difficult to provide proper injection rates due to variable contents of caustic and higher amount of sodium. Neutralization of produced spent caustic is done in a separate plant usually through oxidation in most of the refineries.

b) Fenton Oxidation Further analysis can be done to Fentons process. A kinetics study can be done in the bench scale. For the pilot plant, some modification can be done. Both the reactor and neutralization tank can be equipped with pH controllers. The amount of hydrogen peroxide can be increased to check if sulfide concentration can be lowered. Adsorption bed can be changed to get better results.

6.0 References Hocking, M B. (2005). Handbook of Chemical Technology and Pollution Control (Third Edition), pp 593-636. Hariz, I. B., Halleb, A., Adhoum, N. & Monser, L. (2013). Treatment of petroleum refinery sulfidic spent caustic wastes by electrocoagulation.107. pp 150-157. Waqar Ahmad (2010). Neutralization of Spent Caustic from LPG Plant at Preem AB Gteborg. Chalmers University of Technology, Department of Chemical and Biological Engineering, Sweden. Veerabhadraiah, G., Mallika, N., & Jindal, S. (2011). Spent caustic management : Remediation review. Singapore. Mohamed Al-Jabari. (2012). Spent caustic treatment using advanced oxidation processes.Sharjah, United Arab Emirates.

Legrini, O., Oliveros, E. & Braun, A. M. 1993. Photochemical Processes for Water Treatment, Chemical Reviews, v. 93, p. 671- 698 Neyens, E., Baeyens, J. 2003. A review of classic Fentons peroxidation as an advanced oxidation technique. Journal of Hazardous Materials B, v. 98, p. 3350 V. K. Sharma, T. M. Triantis, M. G. Antoniou, X. He, M. Pelaez, C. Han, W. Song, K. E. OShea, A. A. de la Cruz, T. Kaloudis, A. Hiskia, and D. D. Dionysiou, "Destruction of microcystins by conventional and advanced oxidation processes: A review," Separation and Purification Technology Poyatos, J. M., Muio, M. M., Almecija, M. C., Torres, J. C., Hontoria, E and Osorio, F. 2010. "Advanced Oxidation Processes for Wastewater Treatment: State of the Art," Water, Air and Soil Pollution, vol. 205, pp. 187-204. PHILIPPOPOULOS, C. J., POULOPOULOS, S. G. Photo-assisted oxidation of an oily wastewater using hydrogen peroxide .Journal of Hazardous Materials B, v. 98, p. 201210, 2003 Andreozzi, R., Caprio, V., Insola A., Marotta, R., and Sanchirico, R. 2000. "Advanced oxidation processes for the treatment of mineral oil-contaminated wastewaters," Water Research, vol. 34, pp. 620-628.

HU, Q., ZHANG, C., WANG, Z., CHEN, Y., MAO, K., ZHANG, X., XIONG, Y., ZHU, M. Photodegradation of methyl tert-butyl ether (MTBE) by UV/H2O2 and UV/TiO2. Journal of Hazardous Materials, v. 154 , p. 795803, 2008. , Spent Caustic treatment with OHP Wet Peroxide Oxidation. Internet: http://www.fmcforet.com/Portals/FMCForetTO/Content/Docs/Spent%20Caustic% 20treatment%20with%20OHP.pdf [Feb. 20, 2012].