QATAR UNIVERSITY

Graduate Studies

College of Engineering

CHARACHTERIZATION AND TREATMENT OF SPENT CAUSTIC

FROM AN ETHYLENE PLANT

A Thesis in

Environmental Engineering

By

Hasanat Mohammed Ramadan

© 2013 Hasanat Mohammed Ramadan

Submitted in Partial Fulfillment

Of the Requirements

For the Degree of

Master of Science in Environmental Engineering

December 2013

I
The thesis of Hasanat Mohammed Ramadan was reviewed and approved by the

following:

We, the committee members listed below accept and approve the Thesis of the

student named above. To the best of this committee’s knowledge, the Thesis

conforms the requirements of Qatar University, and we endorse this Thesis for

examination.

Name __________________________________________

Signature _______________________________________ Date__________

Name __________________________________________

Signature _______________________________________ Date__________

Name __________________________________________

Signature _______________________________________ Date__________

II
 ABSTRACT

Spent caustic solution is generated in oil refineries and petrochemical

plants as a result of scrubbing processes where hydrogen sulfide and carbon

dioxide compounds are removed. Spent caustic is considered as one of the most

difficult streams to handle by wastewater treatment plants. Selecting the best

treatment technique is considered to be a critical task, in order to meet the

discharge limit.

The present work aims to find an effective treatment process to treat spent

caustic solution produced from an ethylene plant. Neutralization and

neutralization coupled with oxidation are the two processes studied. Two methods

of oxidation are tested, classical oxidation by using H2O2 alone and advanced

oxidation by using Fenton’s reagent. Applying neutralization alone or

neutralization with oxidation was verified for the achievement of the required

degree of treatment. For the neutralization alone, it was found that the highest

chemical oxygen demand removal achieved was 88 % (1699 mg/l) at pH=1 while

the sulfide removal was 99.8 % ( 9.9 mg/l). For classical oxidation using H2O2,

the best removal was achieved at pH=2.5. The COD % removal was 89 % with a

COD value of 1630 mg/l. Furthermore, the sulfide removal reached a value of

almost 100%. While for the advanced chemical oxidation using Fenton’s process,

the best result was obtained at pH=2.5. The COD % removal was 96 % with a

COD value of 542 mg/l. This was achieved with hydrogen peroxide to ferrous

sulfate ratio of 1: 7.5. The sulfide removal also reached a value of almost 100%.

III
 TABLE OF CONTENTS

Abstract ……………………………………..……………………...……… III

List of Figures ………….….………………..……………………...……… VII
List of Tables ……………………………….……………………...……… VIII
Abbreviation ………………………………..……………………...……… IX
Acknowledgment …………………………………………..……………… X
CHAPTER 1:
1. Introduction ………………...………………………………………… 1
1.1. Spent Caustic ………………………………………………...… 1
1.2. Sources of Spent Caustic Solution from the Ethylene Plant……. 4
1.2.1. Hot section ………………...………………………………… 8
1.2.1.1. Steam Cracker..…… ………….……………………… 8
1.2.1.2. Quenched Tower ..……………………………………. 9
1.2.2. Compression Section ………………………………………... 10
1.2.2.1. Gas Compressors …….………………………………. 10
1.2.3. Cold Section.……………………..….……………………..... 10
1.2.4. Treating (Caustic Tower) ………………………………… 10
1.2.5. Fractionation Section …………………………………….. 11
1.3. Spent Caustic Management Background……………………….. 14
1.3.1. Reduction …………………………………………………… 14
1.3.2. Reuse within the Process ……………………………………. 15
1.3.3. Recycle Outside the Facility ………………………………... 15
1.3.4. Treatment and Disposal ……………………………………... 15
1.4. Spent Caustic Treatment ………………………………………. 16
1.4.1. Biological Treatment of Spent Caustic ……………………... 17
1.4.2. Thermal Treatment ………………………………………….. 18
1.4.3. Chemical Treatment…………………………………………. 20
1.5. Classification of the Chemical Oxidation Processes …………... 22
1.5.1. Classical Chemical Oxidation ………………………………. 22

IV
 1.5.2. Advanced Oxidation Processes (AOPs) …………………….. 25
1.6. Objectives of Present Study …………………………………... 35
CHAPTER 2 :
2. Research Methodology………………………………………………. 37
2.1. Spent Caustic Characteristics …………………………………... 37
2.1.1. Total Suspended Solids and Total Dissolved Solids………… 37
2.1.2. Measurements of Chemical Oxygen Demand (COD)……….. 38
2.2.3. Biological Oxygen Demand (BOD) ……...…………………. 39
2.2.4. Total Sulfide S −2, H2S, HS − by Titration (sulfide above 1 39
mg/l) ………………………………………...………………
2.2.5. Determination of Total SulfideS −2, H2S, HS − (sulfide 0 to 40
800 μg/l)……………………………………………………..
2.2.6. Free Soda and Complete Alkalinity……….………………… 40
2.2.7. Total Petroleum Hydrocarbons (TPH)………………………. 41
2.2.8. Inorganic anions …………………………………………….. 42
2.2.9. Heavy Metals ……………………………..………………… 43
2.2.10. Phenol ………………………………………………….……. 43
2.3. Experimental Setup and Procedure ………………………………. 46
2.3.1. Neutralization ……………………………………………….. 46
2.3.2. Neutralization Coupled with Oxidation …………………….. 48
CHAPTER 3 :
3. Results and Discussion..………………………………….………….. 49
3.1.Neutralization ………...………………………………...…………... 49
3.1.1. Effect of pH on Sulfide Removal……………………………. 49
3.1.2. Effect of Temperature on Sulfide Removal ……….………... 52
3.1.3. Effect of pH on COD Removal……..…………………….… 53
3.1.4. Effect of pH on TDS Removal …………………….…….… 55
3.2.Neutralization Coupled with Oxidation: Classical Oxidation ...…… 55
3.2.1. Effect of Hydrogen Peroxide Concentrations on COD
Removal …………………………………………………….. 56
3.2.2. Effect of Hydrogen Peroxide Concentrations at Different pH

V
 on COD Removal …………………………………………… 59
3.3.Neutralization coupled with Oxidation: Advance oxidation …...….. 63
3.3.1. Effect of pH in Fenton’s Reagent on the Removal of COD.… 63
3.3.2. Effect of Ferrous Sulfate Concentrations on COD Removal... 68
3.3.3. Effect of Hydrogen Peroxide to Ferrous Sulfate Ratio on
COD Removal……………………………………………….. 70
3.3.4. Effect of Hydrogen peroxide to COD ratio on COD
Removal……………………………………………………... 73
CHAPTER 4:
4. Conclusions and Recommendations …..…………………….…...… 76
CHAPTER 5:
5. Future Work ……………………………………...……………….... 79
References ……………………………………………………………… 80

VI
 LISTS OF FIGURES

Figure 1 : Ethylene process flow diagram (PFD) .................................................... 7

Figure 2 : Steam cracker diagram ............................................................................ 9
Figure 3 : Quenched tower ....................................................................................... 9
Figure 4 : Gas compressors .................................................................................... 10
Figure 5 : Treating unit .......................................................................................... 11
Figure 6 : Fractionation unit .................................................................................. 13
Figure 7: Waste management hierarchy ................................................................ 14
Figure 8 : Treatment technologies according to COD contents. ............................ 17
Figure 9 : Oxidation potential ................................................................................ 21
Figure 10: Summarized of the treatment processes of ethylene spent caustic ....... 36
Figure 11 : Experimental schematic diagram ........................................................ 46
Figure 12 : Hydrogen sulfide and pH dependent ................................................... 50
Figure 13: Neutralization of spent caustic ............................................................ 51
Figure 14 : Sulfide % removal at different pH after neutralization ....................... 52
Figure 15 : Sulfide % removal at different temperature ........................................ 53
Figure 16: COD removal % for pH=1,3,5 before neutralization ........................... 54
Figure 17: COD removal % at different pH after neutralization ........................... 54
Figure 18: Effect of pH on TDS removal .............................................................. 55
Figure 19: Blank sample with a) 0.1 H2O2 and b) 1 ml of H2O2 ........................... 58
Figure 20 : COD removal % at different H2O2 concentration ............................... 61
Figure 21 : Sulfide % removal at different H2O2 concentration ............................ 62
Figure 22 : Effect of pH on the COD removal....................................................... 67
Figure 23 : Effect of ferrous sulfate concentration on COD % removal ............... 69
Figure 24 : Effect of hydrogen peroxide to ferrous sulfate ratio on % COD
removal .................................................................................................................. 72
Figure 25 : Effect of hydrogen peroxide to COD ratio on % COD removal ......... 75

VII
 LISTS OF TABLES

Table 1: Spent caustic types and characteristics ...................................................... 4

Table 2 : Physical properties of ethylene ................................................................. 5
Table 3: WAO operational conditions .................................................................. 19
Table 4: Classical chemical oxidation ................................................................... 22
Table 4: Classical chemical oxidation ................................................................... 23
Table 4: Cont Classical chemical oxidation........................................................... 24
Table 4: Cont Classical chemical oxidation........................................................... 25
Table 5: Advanced chemical oxidation.................................................................. 28
Table 5: Cont Advanced chemical oxidation ......................................................... 29
Table 5: Cont Advanced chemical oxidation ......................................................... 30
Table 5: Cont Advanced chemical oxidation ......................................................... 31
Table 6 : Spent caustic characteristics used in this experiment ............................. 45
Table 7 : Effect of hydrogen peroxide concentrations on COD removal .............. 56
Table 8 : Analyses interfere with H2O2.................................................................. 58
Table 9: Effect of H2O2 at different pH on COD removal ..................................... 59
Table 12: Effect of hydrogen peroxide to ferrous sulfate ratio on COD %
removal .................................................................................................................. 71
Table 11: Effect of hydrogen peroxide to COD ratio on % COD removal ........... 74

VIII
 ABBREVIATIONS

NaOH Sodium hydroxide

H2 S hydrogen sulfide
C2H4 Ethylene
C2H6 Ethane
HS- & S-2 Sulfide
SO4 Sulfate
S2- Sulfide
H2O2 Hydrogen peroxide
O3 Ozone
OH• Hydroxyle redical
HO2• Hydroperoxyl
+2
Fe Ferrous
Fe+3 Ferric
FeSO4 /H2O2 Fenton’s reagent
UV Ultra violet
TiO2 Titanium peroxide
DMDS Dimethyl disulfide
COD Chemical oxygen demand
TOC Total organic carbon
BOD Biological Oxygen Demand
TDS Total Dissolved Solids
TSS Total Suspended Solids
TPH Total Petroleum Hydrocarbons
WAO Wet Air Oxidation
CWAO catalytic wet air oxidation
AOPs Advanced Oxidation Processes

IX
 ACKNOWLEDGMENTS

My sincere thanks to my supervisors, Dr. Alaa Al Hawari and Professor

Ibrahim abureesh, who have supported me throughout my thesis work and
provided me with advice, guidance, and continuous encouragement throughout the
work on this thesis.

Special thanks to Dr. Ahmed Al Khatat , senior lab technician of chemical

engineering department, who provided us with his time and knowledge in the lab
measurements. For his sincere help I’m deeply grateful.

Also I wish to express my special thanks to Qatar Pertrochemical

Company (QAPCO) namely Dr. Mabrouk and Mr. Mejali Al Kuwari, who helped
me throughout the period of this research and for the supply of waste samples.

My gratitude is for my loving parents, my husband, and my family for

keeping me motivated during this period of research work.

At the end, my regards to all people who supported me directly or

indirectly during my graduates studies at Qatar University.

X
CHAPTER 1:

1. INTRODUCTION :

1.1. Spent Caustic :

Qatar developed and built a strong industrial sector by employing the

latest technological innovations in their production processes [1]. This eventually

will create a positive and highly beneficial impact on the national economy. Qatar

depends on two main sources of water to meet its need which are conventional

water sources that come from groundwater and non-conventional water sources

that come from desalination of seawater and recycling of treated wastewater [1].

Qatar is working to achieve a “zero liquid discharge” by 2016. The aim of this

project is not to allow any discharge of treated wastewater into water bodies but to

reuse and recycle the produced water. The project is directed by the Ministry of

Energy and Industry with the Ministry of Environment involving various

industries in Qatar [2]. The zero discharge can be mainly achieved by enhancing

the quality of treated waste water where it could be recycled and reused in

irrigation or in operations and production processes.

In Qatar several industrial companies such as Qatar Chemical Company

(Q-Chem), Qatar Petrochemical Company (QAPCO) and Qatar Petroleum (QP)

generate liquid waste that is known as spent caustic solution. Spent caustic is an

industrial waste solution that consists of sodium hydroxide, water, and other

pollutants.

1
 Sodium hydroxide (NaOH) solutions are used in many industries to wash

out acid gases such as hydrogen sulfide (H2S) and carbon dioxide (CO2) from

different hydrocarbon streams [3]. Once these gases react with the majority of

NaOH, a waste solution known as spent caustic will be produced [4]. Spent

caustics are the most difficult class of liquid industrial waste to handle and to

dispose due to the high concentration of pollutants in it [5]. According to the

Environmental Protection Agency EPA under the Resource Conservation and

Recovery Act RCRA used to classify the wastes as hazardous that create potential

harmful impact to the human health and to the environment [6]. The classification

of waste depends on the specific characteristics of the waste itself. The waste is

considered to be hazardous if it exhibits one or more of the four characteristics [6,

7]:

1) Ignitability (D001)

2) Corrosivity (D002)

3) Reactivity (D003)

4) Toxicity (D004 - D043)

Spent caustic could be classified as D003 hazardous waste due to the reactive

sulfide it contains [8]. Also, spent caustic is the highly corrosive due to the high

pH value. Recent environmental regulations have a great impact on the spent

caustic treatment method design since previous usual disposal methods are

becoming legally prohibited [8].

Without treatment, spent caustic stream may cause environmental

problems because of their alkalinity (pH>12), salinity (sodium of 5-12% wt) and

high sulfide S-2 levels exceeding 2-3 wt% [9-11]. However, sulfide can be

2
converted to elemental sulfur and/or sulfate that are preferred finishing product as

it does not represent COD and maybe allowed to be discharged into the

environment [14]. Moreover, spent caustics may contain toxic organo-sulfur

compounds such as methanethiol and aromatic hydrocarbons like benzene [12,

13].

Spent caustics can be classified into many types depend upon the industry

producing it and the source of fuel that fresh caustic wash. Table 1 summarizes

the type of spent caustic and there characteristics. Usually refineries don’t separate

each type of spent caustic and they mix the three types and this is called the mixed

refinery spent caustic [9].

3
Table 1: Spent caustic types and characteristics

Type of Sulfidic Cresylic Naphthenic Ref

spent caustic

Source Ethylene & LPG Gasoline Kerosene & [5]

Diesel

Content High Conc. of High Conc. of High Conc. Of [5]

Sulfides & Phenols & Polycyclic
Mercaptans Cresols aliphatic organic
compounds

Effect after Release gases Foaming and Oil layer & [5]
neutralization settling issue in foaming
the biological

Chemical 5,000-90,000 50,000-100,000 150,000-240,000 [15]

oxygen demand
(COD) (ppm)

Total organic 20-3,000 10,000-24,000 24,000-60,000 [15]

carbon (TOC)
(ppm)

Sulfides (ppm) 2,000-52,000 <1 0-63,000 [15]

Total phenol 2-30 1,900-1,000 14,000-19,000 [15]

(ppm)

1.2. Sources of Spent Caustic Solution from the Ethylene Plant:

In this study spent caustic produced from an ethylene plant will be targeted. In

order to understand where spent caustic will be produced it is important to

illustrate the ethylene process.

Ethylene is the chemical compound with the formula C2H4, because it contains a

carbon-carbon double bond. Ethylene is one of the simplest unsaturated

4
hydrocarbons. Ethylene is a colorless flammable gas with a sweet odor. The

physical properties of ethylene are summarized in Table 2.

Table 2 : Physical properties of ethylene [16]

Property Value

Structural formula

IUPAC name Ethene

Molecular weight 28.05 g/mol

Appearance Colorless gas

Density 1.178 kg/m3 at 15 °C, gas

Solubility in water 3.5 mg/100 ml (17 °C);

Thermodynamic data Phase behavior Solid, liquid, gas

Ethylene is an important building block in the petrochemical industry and its

global production exceeds any other organic compound.

It can undergo many types of reactions which lead to major chemical products.

Ethylene is the raw material to produce a wide range of products such as, ethylene

glycol, ethylene dichloride, polyvinyl chloride, styrene, and polyethylene which is

the common plastic in our daily life.

Ethane is preferred for ethylene production because the steam cracking of ethane

consumes less energy than cracking heavier hydrocarbon. Ethylene process

produce less emissions to the atmosphere because of that it is considered as an

5
environmental friendly process. The process includes a caustic tower which

remove harmful gases such as NOx, mercaptans, H2S and CO2.

Figure 1 shows the process flow diagram of an ethylene plant. Ethylene is

produced from ethane by a sequence of different processing steps which can be

classified as [17]:

 Hot section:

1. Steam Cracker.

2. Quenched Tower.

 Compression section :

1. Gas Compressor.

 Cold section:

1. Treating.

2. Chilling and Fractionation.

6
Figure 1 : Ethylene process flow diagram (PFD)

7
1.2.1. Hot Section

1.2.1.1. Steam Cracker

The Ethane Rich Gas (ERG) supplied from Qatar petroleum refinery contains high

ethane content (65%) and other impurities like methane, hydrogen sulfide (H2S)

and carbon dioxide (CO2) .The ERG gas is treated to remove CO2 and H2S by

using Amine solution to achieve less than 100 ppm. The ERG gas, free of acid

gases, is cooled and refrigerated to –100 oC to separate methane. Finally pure

ethane is sent to cracker unit to produce ethylene.

Figure 2 shows the furnace where the ethane gas is mixed with steam. Steam is

added at controlled rates in order to increase the petrochemical yield and to

minimize carbon deposits (coke) forming in the furnace and heated to about 850
o
C. The ethane is partially converted to ethylene and other hydrocarbons. In this

section Dimethyl disulfide (DMDS) is added in the furnace as a coating to

minimize the coke formation. Also, it is used to prevent over cracking of the gas

to maintain high conversion of ethane to ethylene. This material with high

temperature will generate H2S and CO2 that will be removed later using fresh

caustic soda in the treating section.

8
 Figure 2 : Steam cracker diagram

1.2.1.2. Quenched Tower:

Figure 3 shows the quench tower unit where the effluent (cracked gases coming

from the furnace) is immediately quenched by direct contact with water. The

temperature drop to about 30°C is necessary to stop the cracking reaction. This

quench water is then recovered and re-used.

Figure 3 : Quenched tower

9
1.2.2. Compression Section :

1.2.2.1. Gas Compressors:

Separation of hydrocarbons in distillation column requires the furnace effluent to

be liquefied by increase the pressure of the gas then cool it down.

The cracked gas from the quench tower is compressed in five stages multi-stage

centrifugal compressor as shown in Figure 4.

Figure 4 : Gas compressors

1.2.3. Cold Section :

1.2.3.1. Treating (Caustic Tower) :

The cracked gas stream will contain impurities (acid gases) that need to be

removed. These impurities include carbon dioxide, and hydrogen sulfide that are

generated as a result of addition DMDS in the steam cracker unit. Treatment of

the cracked gas to remove impurities occurs between the fourth stage and the fifth

stage of the compression section and it is treated in a caustic soda washing tower.

Figure 5 shows the caustic tower where in this tower, the gas stream is contacted

with dilute sodium hydroxide as in the following reaction:

10
2NaOH (aq) + H2S (g) Na2S (aq) + 2H2O (1.1)

2NaOH (aq) + CO2 (g) Na2CO3 (aq) + H2O (1.2)

The reason behind selecting the sodium hydroxide to remove the acid gases is its

ability to remove the very small quantities of the acid gases. Then caustic tower

overhead gas that is free from acid gases is treated in dryers to remove moisture

and send to De-ethanizer to separate C3 and heavier components.

Figure 5 : Treating unit

1.2.3.2. Fractionation Section

The cracked gas that is free from acid gases and moisture is cooled down

gradually in the fractionation section. In this section there are four distillation

columns as shown in Figure 6. The first column is the de-ethanizer that separates

out heavy gases such as propane (C3) from the light hydrocarbons (ethylene,

ethane and methane).

11
De-ethanizer overhead is compressed in the 5th stage of compression and passed

through acetylene reactor to remove acetylene. As the gas stream passes the

catalyst the following reaction occurs:

C2H2 (g) + H2 (g) C2H4 (g) (1.3)

Then gas stream is sent to refrigeration chilling to condense ethane. The gas is

cooled and then it liquefies.

The second distillation column is the de-propanizer column. The de-ethanizer

bottom goes to the de-propanizer column to separates C3 hydrocarbon from C4.

The third column is the de-methanizer. This column separates ethylene from the

lighter components which are methane and hydrogen. The methane is then used as

fuel gas.

The fourth column is the C2-splitter that separates ethylene from the ethane. The

ethylene stream is sent to ethylene storage and the bottoms stream which is ethane

is sent back to the cracking furnace.

12
Figure 6 : Fractionation unit

13
1.3. Spent Caustic Management Background:

Waste management is one of the major environmental concerns in the world that

involve solids, liquids and gases [18]. Large quantities of waste cannot be

eliminated but, their environmental impact can be reduced by making more

sustainable use of the waste [18]. The waste hierarchy shown in Figure 7 shows

that disposal is the least favorable option [20, 21]. Regarding spent caustic which

is a liquid waste, disposal is not an option according to Environmental Protection

Agency (EPA) regulations.

Most favorable

Reduce

Reuse

Recycle

Treatment & Disposal

Least favorable

Figure 7: Waste management hierarchy

The management of spent caustic should include:

1.3.1. Reduction:

Source reduction is the best practice when designing a spent caustic treating

process. It is done by generating the least amount of spent caustic while

14
maintaining the desired efficiency of the process. This can be done by using

maximum caustic strength or applying multistage caustic wash [22]. But in case of

reduction spent caustic still will be produced.

1.3.2. Reuse within the Process:

Reuse of spent caustic will result a decrease in the total amounts that it need to be

disposed. According to Ahmad.W (2012), the reuse of spent caustics is suggested

to be used for crude oil neutralization and in the biological wastewater treatment

process to control the pH value [23]. The issue with the reusing spent caustic is

that the concentration of sodium in the spent caustic is not steady and an

appropriate amount is not easy to control [22]. Moreover phenols and napthenates

are more suitable for reuse at controlled concentrations but sulfidic causes odor

issues in this application [22].

1.3.3. Recycle Outside the Facility:

It has been implemented in many refineries in the US and Canada after applying

additional treatment [24]. The valuable compounds from caustic such as sulfide ,

phenols and naphthenic acids can be removed and reused as a raw material in

many industries such as pulp and paper, tannery, mining, wood preservatives and

paint industries [22]. However, this approach may need appropriate cost analysis

before proceeding.

1.3.4. Treatment and Disposal:

Deep well injection is a previous practice used to dispose spent caustic but it is

prohibited nowadays [4]. Recently many treatment methods can be applied and it

15
proofs to be effective. The treatments processes must guarantee the destruction of

the contaminants in order to reach the discharge limit [22]. The removal of

contaminants in liquid solution requires one or more of the available treatment

methods. It is essential to decide on the most appropriate method according to the

characteristics of the liquid solution, cost of the process and volume of the stream

that need be treated [22].

1.4. Spent Caustic Treatment:

The treatment processes of spent caustic must guarantee the elimination of the

pollutants in order to reach the authorized limit for discharge. The elimination of

pollutants in aqueous solution may need one or various basic treatment techniques

depending on the type of compounds and concentration in solution [25]. It is

necessary to choose the most adequate method according to the characteristic of

the effluent.

Numerous efforts have been made to develop and to enhance the treatment of

spent caustic. Treatment methods for spent caustic can be classified as biological,

chemical and thermal processes [22]. According to Andreozzia,R. Caprioa, V.

Insolab, and A. Marottac,R. (1999) the treatment process could be selected

depending on COD concentration [26]. Figure 8 shows the relation between COD

value and the appropriate treatment method [26].

Advanced oxidation processes (AOPs) is selected for COD less than 20 g/l while

wet air oxidation (WAO) is implemented for COD values between 20 and 200 g/l

higher than this value incineration is considered to be the best method [26].

16
 Incineration

WAO
AOPs

0 20 200 300
COD g/l

Figure 8 : Treatment technologies according to COD contents [26].

1.4.1. Biological Treatment of Spent Caustic :

As mentioned before spent caustic stream needs excessive treatment before

discharge. Biological treatment is preferred due to the low cost and the low

environmental impact [27]. The treatment should be done by two steps:

pretreatment followed by biological treatment. The biological treatment can be an

inexpensive disposal option; however there are several drawbacks if it is applied

directly to without pretreatment. These drawbacks are:

1- Noxious odors: Sulfides and mercaptans are highly odors even at the ppb

level. These compounds are considered very toxic and hazardous [28].

2- It is not readily biodegradable: Often spent caustic contains a mixture of

compounds that would limit the biodegradation in the biological treatment

processes [29, 5].

3- Foaming: Spent caustic has compounds that have foaming characteristics

when aerated or agitated during the treatment [29, 5].

17
4- High chemical oxygen demand (COD): This can cause high load to the

biological process [29, 5].

5- PH swings: spent caustic is highly alkaline solution with a pH value that can

reach up to 14 [28].

1.4.2. Thermal Treatment:

1) Wet Air Oxidation (WAO)

Another conventional method is the wet air oxidation (WAO), which is a high

pressure treatment at elevated temperature. Here the oxidation agent is the oxygen

present in the air, which is introduced into the spent caustic as steam. This

reaction can accomplish either mineralization of organics into CO2 and H2O or

destroy complex molecules into simpler molecules that is easier to degrade [30,

31]. The process is very expensive, and due to severe reaction conditions, safety is

a main concern. Although several tests with low pressure has been conducted

without remarkable success [32]. WAO can be classified into three types based on

the temperature implemented to achieve the oxidation. Table 3 shows the three

types of WAO that can be applied to the different kinds of spent caustic.

Using appropriate catalysts for WAO process minimize the severity of reaction

conditions and simply destroy refractory pollutants resulting in reducing capital

and operational cost [33].

The operating cost of catalytic wet air oxidation (CWAO) is around half the non-

catalytic WAO. However, an additional step is required to remove the metal ions

from the treated effluent that would result in increasing operational costs [34].

Catalysts allow overcoming the drawbacks of the WAO; however the discovery of

18
low cost and stable catalysts remains the major weaknesses of CWAO for wide

applications [35].

Table 3: WAO operational conditions [5]

Type of WAO Temperature Pressure Kind of spent caustic

(°C) (psig)

Low 110-120 25 to 100 sulfides in spent caustic

temperature

Mid 200-220 300 to 600 complete treatment of sulfides

temperature and mercaptans , cresylic acids

and naphthenic acids

High 240-260 700 to 1100 complete treatment of sulfides

temperature and mercaptans, cresylic acids

and naphthenic acids

2) Incineration:

Incineration is a process used to convert solid, liquid or gas at elevated

concentration of pollutants into more stable states at higher temperatures [36]. The

economic aspect presents the disadvantage of this process because it requires high

energy cost. In addition toxic emissions that results from this process are high

[22].

19
1.4.3. Chemical Treatment:

1) Neutralization Followed by Air Stripping:

Aeration depends on two fundamental principles: equilibrium conditions and mass

transfer considerations [36]. Equilibrium conditions will identify the limits of the

gas transfer process. Aeration is an efficient method for H2S gas removal. The

function of aeration is not particularly to oxygenate the water, but it is to strip the

dissolved gas (H2S) out of the water by changing the equilibrium conditions of the

water and thus drive the dissolved gas out [36].

Neutralization converts the spent caustic components into their original elements,

such as hydrogen sulfide (H2S), mercaptan sulfur (RSH), phenol and naphthenic

acid. But it requires stripping and additional managing of volatile gases [22]. This

technology is a widely understood method and the simplest and cheapest for the

removal of volatile compounds. However, the effluent stream has elevated COD

concentrations because a major part of the organic component is unaffected by the

stripping process [32].

2) Chemical Oxidation

Chemical oxidation is a method that involves the transfer of one or more

electrons from an electron donor (reductant) to an electron acceptor (oxidant),

which has a higher affinity for electrons. The result of electron transfer is a

chemical change of the oxidant and the reductant [37]. Oxidation technologies

are established to decompose refractory molecules into simpler molecules that

can be further treated by other methods. The mechanism of oxidation works by

transferring electrons from the contaminants to the oxidant. The contaminant is

20
oxidized and the oxidant that accepts the electron is reduced [38]. In natural

waters, chemical oxidation processes also take place due to the presence of

microorganisms that work as natural oxidants [37]. Oxidation reactions generate

chemical species with an odd number of valence electrons known as radicals.

These tend to be highly unstable therefore, highly reactive because one of their

electrons is unpaired. The reactions that produce radicals tend to be followed by

chain reactions between the radical, oxidants and other reactants until stable

oxidation products are formed. The ability of an oxidant to initiate chemical

reactions is measured in terms of oxidative power of an oxidant [39]. The

oxidation potentials are presented in terms of the electro-potential. The electro-

potential based on half-cell reactions [38]. Figure 9 shows the potentials of the

most commonly used oxidizers [40, 41].

Bromine
Oxygen
Chemical oxidant

Chlorine
Chlorine Dioxide
Permanganate
Hydrogen Peroxide
Ozone
persulfate
Sulfate Radical
Hydroxyl Radical

0 0.5 1 1.5 2 2.5 3

Oxidation potential (volts)

Figure 9 : Oxidation potential [1, 2]

21
1.5. Classification of the Chemical Oxidation Processes

Chemical oxidation can be classified into two categories that are described below

in details:

1. Classical chemical oxidation

2. Advanced Oxidation Processes (AOPs)

1.5.1. Classical Chemical Oxidation:

Classical chemical oxidation is a direct chemical oxidation process that is

achieved by the addition of an oxidation agent to the contaminated aqueous

solution to oxidize it. The most common chemical oxidants are chlorine (Cl2),

chlorine dioxide (ClO2), oxygen (O2), persulfate, permanganate (KMnO4), ozone

(O3), and hydrogen peroxide (H2O2). Moreover, advantages and disadvantages of

each oxidant are summarized in the Table 4.

Table 4: Classical chemical oxidation

Chemical Advantages Disadvantages Ref.

Oxidant
Chlorine  Strong oxidant
 Strong disinfectant
generate persistent deposit
 cheap oxidant
 very simple to injected
into the system
 used wildly in the past
 Available in gaseous
form, as Cl2; or as
aqueous solution, sodium
hypochlorite NaOCl; or as
a solid, calcium
hypochlorite, Ca(OCl)2.
o Generate halogenated [42,
DBPs 43]
o Possibly contribute to
odor and taste issues
o Require high dosage of
chlorine
o Create a carcinogenic
organochloride by
products

22
Table 5: Classical chemical oxidation (cont.)
Chlorine  Strong oxidant
dioxide  Strong disinfectant
 Gaseous that is very
soluble in water.
 pH values in the range of
3.5 to 5.5 are preferred
 Used efficiently to taste
and odor for specific types
 Does not generate
halogenated DBPs
 Does not react with
ammonia
Oxygen  Easy to feed in the system
 Does not generate
halogenated by-products.
 Low operation costs
Persulfate  It is much more stable and
it does not react quickly
by nature.
 High oxidation potential
 applicable to wide range
of organics
 It can be catalyzed by
heat, ultraviolet light, high
pH, hydrogen peroxide,
and transition metals
 highly reactive at pH <3,
but it is also highly
reactive at pH > 10
 Fewer mass transfer and
mass transport limitations
o Produces chlorite as an [42]
inorganic DBP
o It might create unwanted
odors
o hard to maintain a
persistent disinfection
o Difficult to handle and
transport because it is
unstable at high
concentrations and can
explode if it exposed to
heat, light.
o Quite weak oxidant for the [42,
majority of water 43]
treatment system.
o Oxygen require certain
operation conditions and
it is not working under
normal temperature and
pressure
o It is requires large
investments in
installations.
o New technology and few [44,
studies are tested in the 46-
field. 48]
o Might degrade soft metal
o Undesirable long lasting
sulfate (SO4-2) By-
products.
23
Table 6: Classical chemical oxidation (cont.)
Chemical Advantages
Oxidant
Permanga  Easy to feed in the system o Produces manganese
nate  Does not generate
halogenated DBPs
 Efficient for certain typeso Can result a pink water
of odor and taste
 Applicable over wide pH
range.
 widely available
 Cheap oxidant
 Easily transport and
handling.
 Less health and safety
problem. (no gas/heat
production)
Ozone  It is a very powerful
oxidizing agent
 Recommended pH =7.5 or
higher
 Applicable to wide range
of organics.
 Very strong disinfectant
 Efficient for taste and
odor
 Does not generate
halogenated DBPs except o Process efficiency is
in bromide-rich waters
 May used to support in the
coagulation and
flocculation
Disadvantages Ref.
[42-
dioxide by product that 44,
should be removed 48]
color if dosage not
controlled
o Limited disinfection
capabilities
o Reduction in the oxidant
efficiency due to the
reaction of the molecules
other than the desired
contaminants. This lead to
increase the need for
oxidant requirements.
o Low oxidation potential.
o Not effective for a wide
range of contaminants.
o Does not create a [42,
persistent disinfectant 44,
residual 45,
o Quietly costly 47,
o generate bromate in 48]
bromide-rich waters
o Ozone can react with a
variety of contaminants,
but it also can react with
many other molecules.
dependent on gas liquid
mass transfer, which is
quite difficult to maintain
due to the low solubility
of ozone in the aqueous
solutions. This Cause non
uniform distribution
through the complete
substance.
o Lack of studies on large
scale operation
24
Table 7: Classical chemical oxidation (cont.)

Chemical Advantages Disadvantages Ref.

Oxidant
Hydrogen  One of the cheapest
Peroxide oxidizers
 It has high oxidizing
potential
 It is water-soluble.
 It does not produce toxins
or color byproducts
 Applicable over a wide
range of organic
contaminants
 Can be combined with
ozone or UV to increase
the efficiency
 It can store, operate and
transport safely.
 Available and relatively
cheap.
o The oxidation process [43-
doesn’t produce by 45,
product 48]
o Not effective for complex
materials
o Mass transfer limitations
between the hydrogen
peroxide with the organics
o Over-oxidation reaction
could happen. So it should
be used in controlled
manner.
o large residence time
should be provided for
H2O2 in the waste stream
because of the low
solubility

From Table 4 it can be seen that chemical oxidants offer a diversity of benefits in

the treatment process. Some are simple and others are more difficult. The classical

chemical oxidation is a multipurpose process that is implemented in many

applications either to treat the wastewater or to improve the quality of water. Each

oxidant has specific advantages that need to be evaluated before employing [41].

1.5.2. Advanced Oxidation Processes (AOPs)

Advanced oxidation processes are considered as promising methods for the

treatment of spent caustic. The mechanism of AOPs is the process of forming

sufficient quantity of highly reactive Hydroxyl radicals (HO•) at near ambient

temperature and pressure. Once it is generated, it can attack the complex chemical

contaminants in water and oxidize most of them [49].When AOPs are applied in

25
controlled conditions, they can reduce the concentration of contaminants from

hundreds of ppm to less than 5 ppb and therefore bringing the COD and TOC to

discharge limits [50].

In some cases these AOPs must be complemented with other treatment techniques

in order to achieve the final treatment level. This leads to a more complex process

and to an increase in the treatment cost [51].

A large number of methods are classified under the AOPs. The generation of the

Hydroxyl radicals are achieved by the use of one or more strong oxidants (H 2O2,

O2, and O3) and/or catalysts (titanium dioxide, transition metal ions ) and/or

energy sources (ultraviolet radiation) [49].

Advanced oxidation processes have several advantages which are [52, 53]:

 Fast reaction rates

 Simple and easy to implement.

 Possible to reduce toxicity and possibly to complete mineralization of

organic pollutants to CO2 and H2O without generating sludge.

 Treatment of various organic compounds at the same time.

While these processes have disadvantages which are [52, 53]:

 Some processes might be high in capital cost

 Need high controlled conditions

 Some applications require quenching of excess peroxide is required.

26
The selection of a certain advanced oxidation process depends on the application.

The selection could be based on the type of compounds to be removed, treatment

objectives, concentrations, site considerations, and cost.

However, it has been observed that none of the methods can be used individually

in treatment applications due to substantially lower energy efficiencies and higher

costs of operation and usually a combination of different AOPs has been found to

be more efficient for the treatment [54, 55]. The main processes found in literature

for producing these radicals are summarized in Table 5. It can be note that UV

system has major drawbacks such as mass transfer limitation, turbidity that can

inhibit UV light diffusion, and some compounds (nitrate) can absorb UV light. All

of these will result lowering process efficiency.

Also, ozone with hydrogen peroxide system is like UV with hydrogen peroxide

system. However, this system is less affected by feed characteristics.

One method can be used to improve contaminants removal is the implementation

of ozone, hydrogen peroxide, and ultraviolet radiation system (O3/H2O2/UV).

However, in this case the cost of treatment system will be huge because of the

usage of the two oxidants. This system is recommended when wastewater

pollutants weakly absorb UV radiation light.

27
Table 8: Advanced chemical oxidation

Chemical Brief description Advantages Disadvantages Ref.

oxidant
UV/O3 When low pressure UV light 1. Supplemented disinfectant 1.
is applied to ozonated water 2. More effective than O3 or UV alone. 2.
hydroxyl radicals are 3. More efficient generating OH radical
generated. Destruction of than H2O2& UV for equal oxidant
organic compounds occurs concentrations. 3.
by hydroxyl radical
reactions coupled with direct 4.
photolysis and oxidation by
molecular ozone. 5.
UV /H2O2 H2O2 is injected and mixed 1. UV decompose H2O2 to 1.
followed by a reactor that produce (2OH) free radicals,
is equipped with UV light. 2. No sludge generation, 2.
During this process, UV is 3. UV/H2O2 process is efficient in
used to cleave mineralizing organic pollutants
the O-O bond in hydrogen 4. No potential for promate
peroxide and generate the formation 3.
hydroxyl radical 5. No off gas treatment requires.
6. Not limited by mass transfer 4.
relative to O3 processes.
5.
Energy and cost intensive process. [57-
Potential for bromate formation but 60]
it can be controlled through
adjustment of pH.
Turbidity can interfere with UV
light.
Ozone diffusion can result in mass
transfer limitations.
May require ozone off gas
treatment.
it cannot utilize solar light as the [57,
source of UV light 60]
H2O2 has poor UV absorption
characteristics because of that
special reactor designed for UV is
required.
Turbidity can interfere with UV
light penetrating
Less stoichometric efficient in
generating OH radical than
O3/H2O2 process.
Interference compounds like
nitrate can absorb UV light

28
Table 9: Advanced chemical oxidation (Cont’d)
Chemical Brief description
oxidant
UV/ TiO2 a titanium peroxide is a
semiconductor absorbs UV
light and causing to
generate hydroxyl radicals.
Perozone (O3 Once O3 and H2O2 are at
+ H2O2 once applied, they react to
form hydroxyl radicals.
Advantages
1. Chemical stability of TiO2 in
aqueous media and high potential to
produce radicals.
2. Easy availability and low price.
3. Possible use of solar irradiation.
4. TiO2 is a cheap, readily available
material
5. TiO2 is capable for oxidation of a
wide range of organic compounds
6. No potential for bromate formation
7. Can be performed at high UV
wavelength than other UV oxidation
processes.
8. No off gas treatment required.
1. Peroxone process is much rapid
than using O3 or H2O2 alone.
2. It is extremely efficient to treat
complex compounds
3. H2O2 is stable in acidic medium
Disadvantages Ref.
1. impossible to achieve uniform [57,
irradiation of the entire catalyst 59,60]
surface
2. Pretreatment is essential to avoid
fouling of the TiO2 catalyst.
3. If TiO2 is added as slurry then a
separation step is required.
4. Need more study to determine the
optimum TiO2 dose
5. Reaction efficiency is highly
depending on pH because of that
close monitoring and control is
required.
6. Require onsite storage or
regeneration method.
7. No full scale exists.
1. Greatly dangerous and should [58,
carefully handle when it is used 59]
and stored.
2. Not very efficient when it is used
to oxidize iron and manganese.
3. Potential to produce byproducts
such as aldehydes, ketones,
peroxides.
4. May require treatment of excess
H2O2.
5. May require gas treatment.
29
Table 10: Advanced chemical oxidation (Cont’d)

Chemical Brief description Advantages Disadvantages Ref.

oxidant
Fenton Fenton’s reagent is 1. Fenton may lead to complete 1. Need to reduce the pH, followed [56,
Oxidation powerful oxidant for destruction of the contaminants by neutralization. 57,59]
H2O2 and organic contaminants .It is under ideal conditions to nontoxic 2. Hazards associated with using
ferrous iron a mixture of ferrous iron compounds. H2O2
(Fe(II)) (catalyst) and hydrogen 2. the iron used can be removed from 3. Hydroxyl radical with high
peroxide (oxidizing agent). the solution concentration might react with the
3. The generation of OH∙ cause to a other species
rapid reaction to many 4. The reaction is exothermic and
contaminants. might cause an increase in the
4. High oxidation potential that can temperature but it can be
target complex organic compounds. controlled.
5. Treatment of both organic and
inorganic substances under
laboratory conditions as well as real
effluents
6. Can oxidize wide range of
contaminants.
7. Iron and hydrogen peroxide are
cheap and safe.
8. Hydrogen peroxide easy to storage
and to handle

30
Table 11: Advanced chemical oxidation (Cont’d)
Chemical Brief description
oxidant
Ultrasound Ultrasound waves are
systems introduced to the
wastewater as compression
and expansion cycles.
Micro-bubbles are
produced .These
compression cycles will
collapse the micro-bubbles
create extremely high
temperature and pressure.
These conditions are
capable of breaking water
molecular producing
hydroxyl radicals.
Advantages
Usually ozone or hydrogen peroxide is
used along ultrasound to promote
hydroxyl radical’s generation which
enhances pollutants’ removal.
Disadvantages Ref
Higher ultrasound frequency will [61,
provide shorter time for the 62]
microbubble to collapse resulting in
lower possibility of hydroxyl radicals
to recombine which result in higher
generation rate of hydroxyl radicals.
The main disadvantages are no
commercial plant using this system
has been built yet and the amount of
oxidant either ozone or hydrogen
peroxide required to increase hydroxyl
radical is large which increases the
cost of operations
31
The treatment of spent caustic by application of Fenton’s method is highly

recommended. As seen in table 4 Fenton’s reaction has several advantages that

make this method to be widely implemented in the treatment processes. It has

high efficiency and its ability to treat various contaminants and can lead to

complete destruction of contaminants [36].

There are many researches that were done to treat refinery spent caustic. It

is very difficult to treat with conventional wastewater processes because of that it

has been incinerated. On the other hand, ethylene spent caustic is highly diluted

than refinery that make it possible to treat and dispose it in a save manner.

Ethylene spent caustic solutions are disposed of through wet air oxidation.

However, the major problem is the exothermal reaction that needs to control the

heat buildup in the process. Also, it is a very expensive process for the treatment.

There are several researches that study the treatment of ethylene spent

caustic by Fenton’s method. Sheu and Weng, (2001) studied a new method of

treatment of spent caustic from a naphtha cracking plant by neutralization

followed by oxidation with Fenton’s reagent. Spent caustic contains high H2S

concentration and some mercaptans, phenols and oil. Over 90% of dissolved H2S

were converted to gas by neutralization at pH=5 and T = 70 oC. The remaining

residual sulfides were oxidized to less than 0.1 mg/l by Fenton’s reagent. The

total COD removal of spent caustic is over 99.5% and the final COD value of the

effluent can be lower than 100 mg/l. As a result, the spent caustic treatment

becomes economical and effective [11]. Moreover, Nunez, et all (2009) studied

electro-Fenton process. The efficiency of the Electro-Fenton process was

investigated as the COD reduction in pure phenol and sulphide solutions and real

32
spent caustic samples. Approximately 97% COD removal was achieved for

sulphide treatment, as the sulphide was highly affected by both the pH reduction

and the oxidation by Fenton’s reagent. In the real spent caustic sample, 93%

COD reduction was obtained. The process designed includes a pH reduction unit

followed by an Electro-Fenton’s reactor. Its advantages regarding safety and

costs make it a process that has to be considered in petroleum refineries [32].

Nowadays, real treatment plant by Fenton’s method exists. The treatment

by Fenton’s is done by a company called “FMC Foret”. They modified Fenton’s

reaction to treat spent caustic and they named the process as Oxidation with

Hydrogen Peroxide (OHP) [62]. However, there are differences between this

method and the Fenton’s reaction. The first difference is the catalyst used in FMC

Foret, the catalyst used is ferrous salt without specifying the type of salt. The

second difference is the operational conditions; Fenton’s reaction operates at

ambient temperature and pressure while FMC Foret operates at mild conditions

[62]. Spent caustic is first pumped to an acidification tank to adjust the pH value

to 3-5 so Fenton’s reaction can take place [11]. After that, the feed is pumped to

raise the pressure to 2-2.5 bar. The pressurized spent caustic is then fed into a heat

exchanger to raise the temperature to 110-120 °C [62]. Then the reactor effluent is

send to a heat exchanger to cool the product. The effluent is then sent to

neutralization tank where the pH is adjusted to a value around 7. As a result of

neutralization, the ferric ion generated in the reaction will precipitate [61]. Finally

the treated effluent is decanted then sent to biological treatment for post

treatment. The main advantage of this process is the ability of treating influents

with different organic content and some inorganic contaminants such as sulfides

33
and mercaptans. Also, COD removal can reach up to 95 % as well as the process

is easy to install with low capital cost [62].

34
1.6. Objectives:

The main objectives of this thesis is to characterize and treat spent caustic

produced from ethylene plants. The treatment process targeted a COD value less

than 1000 mg/l and a sulfide concentration of 2 mg/l. These values were chosen

since these are the limits that should enter the biological process which proceeds

the chemical process.

Two treatment processes will be studied:

1. Neutralization: neutralization will release all carbonates as carbon dioxide

and all sulfides as hydrogen sulfide this in return will result in the COD

reduction.

2. Neutralization coupled with oxidation: oxidation will further reduce the

contaminant’s concentration. Neutralization is applied before the oxidation

because of high concentration of acid gases (H2S and CO2) that would

react with ferric ion causing a loss of iron catalyst

For the neutralization coupled with oxidation two methods will be tested:

1. Classical oxidation by using hydrogen peroxide alone.

2. Advanced oxidation by Fenton’s reagent.

The effect of different parameters on the treatment process will be investigated

namely, pH value, temperature, oxidants and catalyst concentration. The effect of

these parameters on COD and sulfide removal will be measured. Figure 10

summarizes the treatment processes of ethylene plant spent caustic that were

included in this study.

35
Figure 10: Summarized of the treatment processes of ethylene spent caustic

36
CHAPTER 2:

2. RESEARCH METHODOLOGY

2.1. Spent Caustic Characteristics

A spent caustic sample was obtained from Qatar Petrochemical Company

(QAPCO). The pH value and conductivity were initially measured using a pH/

conductivity meter (WTW/Germany). The pH and conductivity values were

13.5-14 and 136.2 ms /cm, respectively.

2.1.1. Total Suspended Solids and Total Dissolved Solids:

Total dissolved solids (TDS), and total suspended solids (TSS) were determined

according to standard method (ASTM D5907) [63]. To measure the total solids a

weighted beaker was filled with 100 ml of spent caustic sample. The sample was

placed inside an oven (Heraeus) at 100 ℃ and left until the sample was

completely dry. The weight of dried sample was measured, subtracting the empty

weight of the beaker it was found that the TS were equal to (85400 mg/l).

To measure the TDS the sample was filtered using a 0.45 𝜇m whatman filter

paper. The filter was then dried at 100 ℃ until completely dry. The weight of the

dried sample was measured it was found that TDS were equal to (77230 mg/l).

TSS was measured by subtracting TDS from TS. It was found that TSS was equal

to (8170 mg/l). All samples were done in triplicates and the mean values were

reported. It was observed that most of the solids in the spent caustic sample were

dissolved solids were they made 90 % of the TS.

37
2.1.2. Chemical Oxygen Demand (COD):

Chemical oxygen demand was measured by HACH Program [64]. This method

determines COD depending on the quantity of consumed oxygen by certain

impurities in water based on the reduction of dichromate solution. Three main

solutions were prepared for this test. The stock COD standard solution was

prepared by dissolving 0.425 g potassium hydrogen phosphate in 400 ml distilled

water which was then diluted to 500 ml to get 1000 mg/l COD. Standard

solutions with known concentrations of 100, 300, 500, 700, 900, 1000 mg/l COD,

were then prepared. The second solution is the digestion solution which was

prepared by adding 10.2 g potassium dichromate (K2Cr2O7) standard grade, 167

ml H2SO4 and 33.3 g powdered mercuric sulfate (HgSO4) to 500 ml of distilled

water, dilute and complete to 1 liter. The third solution is the catalyst solution that

was prepared by adding 5.5 g of powdered silver sulphate (AgSO4) to 1 kg of

concentrated sulfuric acid (H2SO4). After that, 2.5 ml of samples, standards and

blank were added to the cultured tubes. Next 1.5 ml of the digestion solution and

3.5 ml of the catalyst solution were added to the cultured tubes. The tubes were

caped tightly and shacked to mix the layers. Then tubes were placed in (Heraeus)

oven at 150 ℃ for 2 hours. After that, the samples were allowed to cool for about

20 minutes until reaching room temperature. Blank and standard tubes were

placed in the (Varian) UV- spectrophotometer to calibrate the device before

measuring COD values.

38
2.1.3. Biological Oxygen Demand (BOD):

Biological oxygen demand was measured by standard method (SM 5210 B) [65].

The BOD test measures the dissolved oxygen consumed by microbial life while

assimilating and oxidizing the organic matter present. A sample has brought to the

desired temperature 20°C and mixed very well to homogenize the sample. 94 ml

of sample has poured into sample bottle. To inhibit nitrification three drops of

Ally Thiourea or ATH were added because BOD measurement shouldn’t include

the oxygen consumption by nitrifying bacteria. Clean magnetic stirring rod was

added in the bottle. 3-4 drops of 45% potassium hydroxide solution was added to

seal gasket. This will absorb the CO2. After that, the seal gasket was inserted in

the neck of the bottle and the device was switched. The Oxidirect has an optional

auto start function that enables it to start. BOD bottle was placed in position into

the bottle rack .The incubation period for the sample is 5 days at 20°C. After five

days the BOD value was found around 431 mg/l.

2.1.4. Total Sulfides (𝐒 −𝟐 , H2S, H𝐒 − ) (sulfide above 1 𝐦𝐠/𝐥)

Total sulfides were measured by titration method [66]. The titration method is

applicable to the measurement of total and dissolved sulfides for water in

concentrations above 1 mg/l [66]. Sulfide is reacted with an excess of iodine in

acid solution, and the remaining iodine is then determined by titration with

sodium thiosulfate.

Approximately 0.5 ml of a sample was taken into 100 ml conical flask and diluted

with dematerialized water until 100 ml. Then 10 ml of 0.010N iodine was added

39
and mixed .Without delay 10 ml of concentrated hydrochloric acid HCl was

added and the sample was shacked vigorously. Immediately sample was titrated

with 0.010N 𝑁2 𝑆2 𝑂3, till faint yellow appear .Then starch was added as an

indicator and titration was continued until the blue color disappeared and became

like light-straw color. A blank of approximately 100 ml dematerialized water was

prepared and carry it through the same procedure as the sample. Then calculate

total sulfide using equation 2.4.

𝑆 −2 (mg/l) = (1000/ml of sample) × 0.1603 × (ml blank –ml sample) (2.1)

2.1.5. Determination of Total Sulfide (𝐒 −𝟐 , H2S, H𝐒 − ) (sulfide 0 to 800 𝛍𝐠/𝐥):

The Methylene blue method by HACH Program is used to measure total sulfide

(0 to 800 𝜇𝑔/l) [64]. 25 ml of sample was measured and filled in the sample cell.

Also, a blank was prepared by measure 25 ml of dematerialized water into second

sample cell. Then 1 ml of sulfide reagent (1) was added to each cell and swirl to

mix. After that, 1 ml of sulfide reagent (2) was added to each cell. Immediately

swirl to mix. The blank was placed and zero key was pressed. Then the prepared

sample was placed in the cell holder. The light shield was closed then result is

displayed.

2.1.6. Free Soda and Complete Alkalinity:

To determine the quantity of available free soda and complete alkalinity in

solution by manual titration was performed. This method is applicable for very

low free soda to 0.1% and complete alkalinity as low as 0.1 % [64].

40
A flask was cleaned by distilled water and dried with clean paper. The weight of

empty flask was measured using Aeadam sensitive balance. With clean pipette 10

ml of sample was taken and weighted. Then 100 ml distilled water and three

drops of phenolphthalein were added. After that, titrate it against 1N sulfuric acid

till the pink color of solution changes to colorless. Then three drops of methyl

orange was added to the colorless solution in the flask. Titration was continued

against 1N sulfuric acid till yellowish colored solution changes to orange color.

Calculate the Free soda equation (2.2):

4 (𝑉1 (6.8 𝑚𝐿)−𝑉2 (9 𝑚𝐿))

Free soda in % wt = (2.2)
𝑝(10.19)

4 (𝑉1 (6.8)+𝑉2 (9))

Complete alkalinity % wt = (2.3)
𝑝 (10.19)

Where:

P: is the weight of sample

V1: is the volume of H2SO4 used in titration after addition of phenolphthalein

V2: volume of H2SO4 used in titration after addition of methyl orange

Calculate the total alkalinity by equation 2.3

2.1.7. Total Petroleum Hydrocarbons (TPH)

Total petroleum hydrocarbon (TPH) is a measure of concentrations mineral oil,

hydrocarbon oil, extractable hydrocarbons and oil and grease. TPH was measured

by standard method (ASTM D7678) [67]. This method covers the range between

0.5 to 1000 mg/l. 500 ml of the sample was taken in flask and sulfuric acid drops

41
were added to the sample until the pH value reached 2. Then 10 ml of solvent

cyclohexane and magnetic stirrer bar were added to the sample. The sample was

left in the magenitic stirrer to around an hour. After that, the mixture was

transferred to a separation funnel and allowed to separate. The aqueous layer was

run through the separation funnel and the upper oil layer was left in the funnel.

For the calibration (1000, 2000, 3000, 4000 mg/l) sample by weight was prepared

a 1.0, 2.0, 3.0. 4.0 g Tetradecane into a 100 ml volumetric flask then filled to the

mark with cyclohexane .Then the flask was shacked to get well mix of liquid.

The CaF2 cell was installed and carried out scan for blanks, standards and

samples. Using Spectrum Beer’s software, the concentration of the total

petroleum hydrocarbon (TPH) in the water samples is calculated. The software

uses the absorption data of the samples and standards obtained by FTIR analysis

to measure the concentration of TPH. First, the standards concentrations (1000,

2000, 3000, 4000 ppm) are measured and a calibration curve is generated. The

calibration curve is then used by the software to quantify and measure the TPH

content in the tested water sample.

2.1.8. Inorganic Anions

Inorganic anions were measured by standard method (EPA 300.1) [68] .This

method covers the determination of inorganic anions such as bromide (Br), nitrite

(NO2), nitrate (NO3) , fluoride (F-), sulfate (SO4), chloride (Cl-), ortho-phosphate

(H3PO4). Dilution of the sample was done by taking 1 ml of spent caustic sample

in 500 ml flask and filling it with distilled water to the mark. Then a small volume

42
of sample was inserted in the special tube for the device. Then the sample was

injected into a Metrohm 850 professional ion chromatograph after calibration.

The sample was analyzed and results were collected from computer.

2.1.9. Heavy Metals

Heavy metals were measured by standard method (EPA 200.7) [69]. Inductively

Coupled Plasma (ICP) device is used to analyze the major, minor, and trace

elements in sample. It need relatively low sample size <10 ml for analysis and

measures heavy metals up to 10 ppb or lower.

This was done by taking 1 ml of sample in 100ml flask and fills it with distilled

water 100 ml. I Cap 6000 series Thermo Scientific device was used .The plasma

was ignited and an appropraite incident power with minimum reflected power was

selected. The instrument was allowed to become thermally stable before

beginning which took around 30-60 min. The samples were inserted in the auto

sampler rack and the work sheet for samples were filled.

2.1.10. Phenol

Phenols were measured by standard method (EPA 420.1) [70]. In this method

phenolic materials react with 4-aminoantipyrine in the presence of potassium

ferricyanide at a pH of 10 to form a stable reddish-brown colored. The amount of

color formed is a function of the concentration of phenolic material. Also,

distillation is necessary to be done to eliminate any interference materials.

About 500 ml of the sample was measured into a beaker. 5 ml of copper sulfate

was added to the sample and pH of the sample was lowered to approximately 4 by

43
using phosphoric acid solution 85% H3PO4. This is done to inhibit the biological

degradation. Around 450 ml of distilled sample was collected then the distillation

was stopped, and 50 ml of water was added to the flask and resume distillation

until 500 ml have been collected. Standards were prepared by Dilution of 10 ml

stock phenol solution to 1 liter with distilled then series of standards were (0, 50,

100, 200, 500, and 1000) were done in 100 ml volumetric flasks.

Buffer solution (NH4Cl in NH4OH) was added to 100 ml of distillate and

standards until the pH of the sample and standards should be 10 ± 0.2. Then 2.0

ml of Aminoantipyrine solution was added and mix Also 2.0 ml of potassium

ferricyanide solution was added and mix. After 15 minutes read absorbance using

spectrophotometer, at 510 nm.

The main characteristics of the ethylene plant spent caustic are represented in

Table 6. Average values for three samples are recorded. The characteristics of

spent caustic solution produced from ethylene plants are different than those for

spent caustic solution produced from any other petrochemical industry. The

impact of these different characteristics on the several treatment processes will be

studied. Sheu and Weng (2001) found that the pH value for a spent caustic

solution produced from an ethylene plant was around 13.5–13.7 which is close to

the values measured in this study. However, phenols concentration was 300 mg/l

which is very high compared to the analyzed sample where phenols concentration

was almost zero. Phenol concentration was found 0.1mg/l which is less than

discharge limit which is 0.5mg/l [72]. In addition Forbess et al. (2009) found that

COD concentration was 11700 mg/l which is close to the analyzed sample in this

study where it was 15000 mg/l. Moreover, It was found that sulfate concentration

44
was 507mg/l and the sulfide concentration was 4990 mg/l [15]. While for the

analyzed sample the sulfate concentration was 8200 mg/l and the sulfide

concentration was 5200 mg/l. Non of the previous studies studied the treatment

process of spent caustic produced from ethylene plants. The different

characteristics of such spent caustic solution would highly affect the treatment

process.

Table 12 : Spent caustic characteristics used in this experiment

Parameters Unit Average Value

COD mg/l 15000
BOD mg/l 431
pH 13.5
Conductivity ms/cm 136.2
Oil & grease mg/l 68.62
Sulfide mg/l 5200
TS mg/l 85400
TDS mg/l 77230
TSS mg/l 8170
Sulfate mg/l 8200.82
Chloride mg/l 14.172
Phenol mg/l 0.1
Heavy metals mg/l traces
Free soda wt % 1.804
Total alkalinity wt % 3.529

45
2.2. Experimental Setup and Procedure

2.2.1. Neutralization:

2
3
4

1- Spent caustic sample 2- Burette

3- Mixer 4- Thermometer
5- pH meter 6- Hot plate
Figure 11 : Experimental schematic diagram

Figure 11 shows the experimental setup. Temperature and pH were continuously

measured using (WTW/Germany). In order to ensure homogenous condition in

the reactor the solution was continuously mixed at 200 rpm. The degree of stirring

was kept mild as any excessive stirring lead to excessive foaming as a result of

presence of some of polycyclic aliphatic organic compounds and some phenols

and cresols [5]. The acidification reaction temperature was maintained by a

thermal hot plate. Also, a mercury thermometer was placed within the reactor to

monitor the temperature increase throughout the reaction. The selection of the

chemicals used for the neutralization of an acid or base is almost as important as

46
the design of the neutralization system. There are many considerations ranging

from health and safety to cost and convenience of operation. Strong acid sulfuric

acid is almost universally used for neutralization reactions that it is used in this

step to lower the pH from 1 to 8. Sulfuric acid is used because of its availability at

concentrations ranging from 0% to 98% and it is the least expensive acid to use. It

is easier and safer to use than HCl or HNO3 [72].

The experiments were conducted in a 250 ml round bottom flask filled with 150

ml of the spent caustic sample. The flask is made of pyrex glass equipped with

two 25 ml burettes, one filled with 98% wt concentrated sulphuric acid (panreac)

and the other filled with 5.0 M sodium hydroxide solution. Sulphuric acid was

added to each sample to maintain different pH values (1, 3, 5, 7, and 8). At each

pH value temperature should maintain 30, 60, and 90 ℃. Samples were collected

from the reactor for COD, sulfide and TDS analysis. After that, for the pH of 1, 3,

& 5 the samples were immediately neutralized to a pH of 7 using sodium

hydroxide since the suitable condition for to the biological process is around pH =

7 to 9 [73]. After adjusting the pH, samples were taken for COD, TDS and sulfide

analysis. Total dissolved solids (TDS) measurements were done by filtering and

evaporating spent caustic solution and measuring the mass of residues left. Also

to check electrical conductivity was measured by conductivity meter. TDS is

directly related to the concentration of dissolved ionized solids to create and

conduct an electrical current [74].

47
2.2.2. Neutralization Coupled with Oxidation:

The Fenton oxidation technology works at ambient conditions however with the

exothermic neutralization reaction the reactor temperature maintained about 65℃

by hot plate. This is also the reaction temperature; observed in the full-scale

neutralization unit of ethylene plant .A mercury thermometer was also placed

within the reactor to monitor the temperature increase throughout the reaction.

Batch time was fixed at 60 minutes. The batch time was selected given that

almost 90% of the COD removal occurs within the first ten minutes of the

reaction [75]. The flask is equipped with three 25 ml burettes .The first burette is

filled with sulfuric acid to adjust the pH of the samples to 1.5, 2.5, and 3.5. The

second burette is filled with Fenton reagent 30 wt% lab grade hydrogen peroxide

(panreac) for the oxidant regent. Ferrous sulfate catalyst is added before adding

the oxidant reagent as solid and enough mixing is applied. And the third burette is

for the 5.0 M sodium hydroxide to neutralize the sample after oxidation. The

sample is neutralized to a pH of 7 to 9 since the suitable condition for to the

biological process is around this pH value [74]. After adjusting the pH samples

were taken for COD and sulfide analysis.

48
CHAPTER 3:

3. RESULTS AND DISCUSSION

3.1. Neutralization

3.1.1. Effect of pH on Sulfide Removal:

The removal of H2S by neutralization is defined by Henry’s Law which is

commonly associated with dilute solutions. It relates the concentration of gas in

water to the partial pressure of the gas above the liquid [76]. For H2S removal it is

necessary to verify the quantity exists in the water which is a function of pH and

temperature.

According to Arrhenius's, an acid is a substance that dissociates in aqueous

solution, releasing the hydrogen ion H+ [77]. The equilibrium constant for this

dissociation reaction is known as a dissociation constant pKa [78]. Hydrogen

sulfide exists in equilibrium in three different forms H2S, HS- , S-2 as shown in

reactions (3.1) and (3.2):

H2S ↔ HS- + H+ pKa=7.1 (3.1)

HS- ↔ S-2 + H+ pKa=14 (3.2)

Acidification plays a significant role to prepare the spent caustic feed for further

treatment. Contribution of acidification in treatment comes from releasing acidic

compounds (total sulfide) that are captured by alkaline compounds (spent caustic)

[5].

As shown in Figure 12 hydrogen sulfide varies with varying the water pH. At a

pH equal to 7.0 approximately 50% of the total sulfide is H2S while 50% is

49
present as HS-. At a pH equal to 8.0, only 10% of total sulfide is present in the

H2S form while the remaining 90% is HS- [77].

Figure 12 : Hydrogen sulfide and pH dependent

In this experiment adjusting the pH of the spent caustic sample to 7, an excessive

foaming was formed as shown in Figure 13-a. The foaming is due to the presence

of containing some of polycyclic aliphatic organic compounds and some phenols

& cresols [5]. Also, an extreme color change was observed as shown in Figure 13-

b and very strong odor as rotten eggs was noticed because of the presence of

sulfide compounds in the spent caustic sample.

50
 pH=1 pH=3 pH=5 pH=7 pH=8

a) Foaming of spent caustic formed (b): color changed for neutralized

after addition of acid Spent caustic at different pH values

Figure 13: Neutralization of spent caustic

Starting the experiments with a reaction temperature of 60oC since this

temperature is observed in the full-scale neutralization unit of ethylene plant. As

shown in Figure 14 the best removal percentage of sulfide was at a pH value

equal to 1 where 99.8 % of sulfides were removed from solution. Whereas the

least removal percentage was At pH= 8. The amount of sulfide remaining in the

treated solution was 9.9 mg/l at pH=1 and 63.5 mg/l at pH=8. As the pH

increased the removal percentage of sulfides decreased. This is due to the fact that

sulfides are mainly in the form of H2S gas at low pH values as shown in Figure

12. At a pH value equal to 7 approximately 50% of the total sulfide is H2S while

50% is present as HS-. Similar results were obtained by Weng and Sheu (2001)

where they found that by in the neutralization of spent caustic, the reduction in

sulphide concentration is significant when reducing the pH to around 4 to 5 [11].

Decreasing the pH below 4 has a little effect on the reduction of sulphide

concentration.

51
 100.00
99.81 99.44 98.78
90.00 95.18 92.56
80.00
Sulfide removal %

70.00
60.00
50.00
40.00
30.00
20.00
10.00
0.00
pH=1 pH=3 pH=5 pH=7 pH=8
pH

Figure 14 : Sulfide % removal at different pH after neutralization

3.1.2. Effect of Temperature on Sulfide Removal:

After the effect of pH on the sulfide removal has been studied the effect of

temperature on the removal should be also investigated. From Figure 14 the best

removal was found at pH value of 1 because of that the effect of temperature at

this pH value is selected to be tested. Three temperatures values have been

selected to be performed in these experiments which are 30, 60, and 90 oC. When

the neutralization was carried out at pH=1, the best removal achieved at

temperature of 60 ℃ with percentage removal reached to 99.81 as shown in

Figure 15. While at temperature of 30 ℃ and 90 ℃ the removal of sulfide was

around 97.8% and 98.5 % which are lower than the removal at 60℃.

52
 100
99.81
98
98.50
97.80
96

94
Sulfide % Removal

92

90

88

86

84

82

80
T=30 C T=60 C T=90 C
Temperature

Figure 15 : Sulfide % removal at different temperature

3.1.3. Effect of pH on COD Removal :

In these experiments the effect of neutralization reaction on the removal of COD

from the spent caustic is shown in Figure 16 and 17. At the beginning the pH of

spent caustic samples were dropped to 1, 3, 5, 7, and 8 at temperature of 60 oC by

using concentrated sulfuric acid. After that, samples 1, 3, and 5 were neutralized

again by using sodium hydroxide to pH 7 to 8. While for samples 7 and 8 the pH

is left the same. This step is done due biological discharge limit. Figure 16 shows

that the removal of COD reached around 60% for the samples 1, 3, and 5. While

Figure 17 shows the removal of COD after the neutralization to pH=7-8 for pH=1,

3 and 5 reach around 80 to 88%. The data indicate that the average total COD

removal by neutralization was about 85% at pH between 1 to 5. From the results,

the increases on COD percentage removal were due to the hydrogen sulfide

53
removal from spent caustic solution. The remaining compounds in the treated

solution are mainly hydrocarbons compounds [5].

T= 60 C
100.00
90.00
80.00
70.00
COD % removal

60.00 64.28
59.01 59.10
50.00
40.00
30.00
20.00
10.00
0.00
pH=1 pH=3 pH=5

PH
Figure 16: COD removal % for pH=1,3,5 before neutralization

T=60 C
100.00
90.00
88.67
80.00 83.99
80.33
70.00 73.45
COD % removal

60.00
50.00 53.25
40.00
30.00
20.00
10.00
0.00
pH=1 pH=3 pH=5 pH=7 pH=8
pH

Figure 17: COD removal % at different pH after neutralization

54
3.1.4. Effect of pH on TDS Removal:

The expected impact on TDS from addition of various chemical dosages could be

straight forward such as neutralization with acid or base to more complexes [79].

Addition of chemical will almost always increase TDS while the biological

treatment alone will lower the TDS [79]. Figure 18 shows the effect of pH on

TDS % removal after addition of acid to spent caustic samples to pH 1, 3, 5, 7 and

8. The results show that the change in the pH as a function of chemical addition

has a very slight effect on TDS.

100.00 pH

90.00
TDS % removal (mg/l)

80.00
70.00
60.00
50.00 53.32 53.26 52.91 52.39 52.38
40.00
30.00
20.00
10.00
0.00
pH=1 pH=3 pH=5 pH=7 pH=8
pH

Figure 18: Effect of pH on TDS removal

3.2. Neutralization Coupled with Oxidation: Classical Oxidation

Oxidation by hydrogen peroxide is a complex reaction controlled by different

variables, such as pH value, temperature, peroxide concentration and reaction

55
time [38]. These variables control the rate of the reaction, the consumption of

hydrogen peroxide and the end products formed [80]. Hydrogen peroxide is a

multipurpose oxidant for many systems. It can be applied to the system directly or

with a catalyst. Incase catalyst is employed then this process is known as an

advanced oxidation process.

3.2.1. Effect of Hydrogen Peroxide Concentrations on COD Removal:

The effect of hydrogen peroxide H2O2 concentration on COD removal in a spent

caustic solution was studied. Different hydrogen peroxide concentrations were

added to the spent caustic samples at a pH value of 2.5 and 60 minute reaction

time. Treated samples were neutralized to a pH of 7 by 5.0M sodium hydroxide

solution. The samples were then decanted and analyzed for COD.

It was observed that after the addition of H2O2 to both spent caustic samples and

the blank samples that an increase in the COD value more than the original

sample occurred as indicated in Table 7. For the blank sample, the device could

read the COD reading for 0.1 dosage of H2O2. However, it is out of range when

the dosed increase to 1ml and 5ml. Furthermore, for the spent caustic sample, the

COD value became more than the initial value.

Table 13 : Effect of hydrogen peroxide concentrations on COD removal

Volume H2O2 Blank Spent caustic

(ml) (ml) COD (mg/l) COD (mg/l)

1 50 0.1 1420 3175

2 50 1 Over the range 11525

3 50 5 Over the range 18765

56
This could be due to the hydrogen peroxide interference with analytical

procedures which caused the increase the COD values [81].

When potassium dichromate is added to the hydrogen peroxide in the solution

that is acidified with sulphuric acid, a green color appears as shown in Figure 19-

a. It is mainly due to the Cr+3 ions formed by the reduction of potassium

dichromate as in equation 3.3 [82].

K2Cr2O7 + 3H2O2 + 4H2SO4 → K2SO4 + Cr2 (SO4)3 + 7 H2O +3O2 (3.3)

Also, the ratio of the COD to the concentration of hydrogen peroxide is important.

The reason behind that is the reaction of the dichromate ions and hydrogen

peroxide in an acidified solution proceeds by a more complex reaction mechanism

as well as a reaction equation (3.3).

According to Kang, Cho and Hwang (1999) [82], peroxodichromic acid which is

blue in color is formed as shown in Figure 19-b:

H2Cr2O7 +5H2O2 → H2Cr2O12 + 5H2O (3.4)

This compound immediately reacts with hydrogen peroxide and forms chromic

oxide (Cr2O3) as follows: [82]

H2Cr2O12 + 8H2O2 → Cr2O3 + 9H2O + 8O2 (3.5)

57
 (a ) (b)

Figure 19: Blank sample with a) 0.1 H2O2 and b) 1 ml of H2O2

Hydrogen peroxide has three properties which are an oxidizing agent or reducing

agent or liberates oxygen that may cause it to interfere with analytical procedures.

Table (8) below lists those specific analyses in which H2O2 is known to interfere

with the analytical test [81].

Table 14 : Analyses interfere with H2O2 [81]

Analysis Procedure Effect

Biochemical Oxygen Demand Oxygen Uptake Reduces Value

(BOD)

Chemical Oxygen Demand Dichromate Increases Value

Digestion
(COD)

Sulfide Methylene Blue Reduces Value

Sulfide Iodine Titration Reduces Value

Several methods are commonly used to remove interferences due to hydrogen

peroxide residual. The selection of the most suitable method is based on the

desired analytical method [81].

58
3.2.2. Effect of Hydrogen Peroxide Concentrations at Different pH on COD

and Sulfide Removal:

In order to remove the interference of H2O2 on COD, elevated pH and

temperature was used [81]. Treatment of spent caustic sample with high

temperature should be maintained around 65℃. However in the real plant the

temperature of spent caustic stream is around 65 ℃ therefore, there is no

additional heating is required. Then neutralize the treated samples to high pH to

around 8-9. Then samples were allowed to settle before being tested for the COD

this can be done by centrifuging the samples. The liquid is decanted for analysis

of COD and sulfide test. This process may be further accelerated by addition of

iron compounds [45].

As shown in the Table 9 the interference of H2O2 with COD was minimum after

applying high temperature (less than 65℃) and neutralize to pH value of 7-9.

Table 15: Effect of H2O2 at different pH on COD removal

Volume H2O2 H2O2 Initial pH=3.5 pH=2.5 pH=1.5

(ml) (ml) mMole/l COD COD COD COD
(mg/l) (mg/l) (mg/l) (mg/l)

1 50 0.01 1.96 15000 2336 1702 1790

2 50 0.1 19.54 15000 2209 1630 1734

3 50 0.5 96.93 15000 2702 2007 1800

4 50 1 191.96 15000 2812 2380 1831

59
As shown in Figure 20, at the beginning when the spent caustic samples were

neutralized to pH 1.5, 2.5, 3.5 the COD removal reach around 87%, 84%, and 80

%. Then when H2O2 is started to be implemented in the system, it can be noticed

that COD percentage of removal starts to increase. The COD removal increases as

the concentration of hydrogen peroxide increase due to the generation of hydroxyl

radicals. COD % removal keeps on increasing until it reaches a maximum value

and then it starts to decrease. The maximum COD % removal is around 89% at

pH=2.5 and hydrogen peroxide concentration 0.1 ml. Above this concentration,

COD % removal decreases as the concentration of hydrogen peroxide increases.

COD decreases at high concentration of hydrogen peroxide because of the

scavenging effect of hydrogen peroxide [76]. Hydrogen peroxide is the oxidant of

Fenton’s reaction. However, at high concentration of hydrogen peroxide,

hydrogen peroxide tend to react with hydroxyl radical to produce a weaker

radicals HO2• as was shown in reaction (3.6). Reactions (3.6) and (3.7) will

compete and at high concentration of hydrogen peroxide, scavenging of hydroxyl

radical will dominate [83]. As a result, hydrogen peroxide is not fully utilized to

generate hydroxyl radicals. This will decrease the efficiency of the process as

more hydrogen peroxide is needed to achieve the desired COD removal. This

reaction can also imply that for the same volume of hydrogen peroxide, higher

COD removal can be achieved if the concentration of hydrogen peroxide is kept

low [83].

OH• + H2O2 → H2O + HO2• (3.6)

Fe+2 + H2O2 → Fe+3 + OH• + OH− (3.7)

60
 100
pH=1.5
98 pH=2.5
96 pH=3.5

94
COD % removal

92
90
88
86
84
82
80
0 50 100 150 200 250
H2O2 mMole/L

Figure 20 : COD removal % at different H2O2 concentration

H2O2 can control sulfides in two ways destruction by oxidizing sulfide to

elemental sulfur or sulfate ion and prevention by providing dissolved oxygen that

inhibits the septic conditions that lead to biological sulfide formation. The

reaction between sulfides and hydrogen peroxide depends greatly on the pH of the

solution. At low pH values, sulfide exists primarily as molecular hydrogen

sulfide, H2S which reacts on a 1:1 (w/w) basis with hydrogen peroxide to form

elemental sulfur. This is the most efficient use of hydrogen peroxide. At neutral

pH, H2S and HS– coexist and hydrogen peroxide reacts at a 1.5:1 (w/w) ratio with

the sulfides. At alkaline pH, it takes four times as much hydrogen peroxide to turn

the S-2 ion into sulfate. The reactions that occur in each pH range are shown in

equation (3.8 - 3.10) [80]:

Acid pH:

H2S + H2O2 → Sº + 2H2O (3.8)

61
Neutral pH:

H+ + HS– + H2O2 → Sº + 2H2O (3.9)

HS– + 4H2O2 → SO4-2 + 4H2O + H+ (3.10)

Alkaline pH:

S-2 + 4H2O2 → SO4-2 + 4H2O (3.11)

In order to use less chemical oxidant spent caustic is neutralized to become an

acidic solution. Therefore, sulfide is converted to hydrogen sulfide and oxidant

will complete the removal of sulfide.

By using the H2O2 the concentration of sulfide is very low because of that

Methylene blue method by HACH program is used to measure total sulfide (0 to

800 𝜇𝑔/l). As shown in Figure 21 almost 100% removal of sulfide was achieved.

pH=3.5
100 pH=2.5
98 pH=1.5
96
Sulfide % removal

94
92
90
88
86
84
82
80
0 50 100 150 200 250

H2O2 mMole/l

Figure 21 : Sulfide % removal at different H2O2 concentration

62
3.3. Neutralization coupled with Oxidation : Advanced

Oxidation Process using Fenton’s Reagent

Oxidation by H2O2 alone is not effective for high concentrations of contaminants.

[84]. Because of that transition metal, ozone or UV-light is implemented to

accelerate the reaction rate of H2O2 decomposition to form hydroxyl radicals. The

oxidation capability of Fenton’s reaction comes from the production of hydroxyl

radical. Fenton’s reagent is a reaction between ferrous ion with hydrogen

peroxide resulting ferric ion, hydroxyl radical and hydroxyl anion according to

the reaction (3.12 ) [85-87].

Fe+2 + H2O2 → Fe+3 + OH• + OH− (chain initiation) (3.12)

This reaction is the chain initiation of Fenton’s reaction .The ferrous ion function

is to initiate and catalyze the decomposition of hydrogen peroxide that causes the

generation of hydroxyl radicals. The generation of hydroxyl radicals follow

complex chain reaction [88]. Once the ferric ion is formed, it reacts with the

hydrogen peroxide resulting decomposition into water and oxygen. Also, ferrous

ions and radicals are also formed according to the following reactions [89, 90]:

Fe+3 + H2O2 ↔ Fe–OOH+2 + H + (3.13)

Fe–OOH+2 → HO2• + Fe+2 (3.14)

Reactions (3.13) and (3.14) are known as Fenton-like reaction. Moreover, Fe–

OOH+2 is an intermediate that can decompose to produce HO2 radical. HO2

radical can oxidize contaminants; its oxidation potential is much less than

hydroxyl radical. Also, several chain reactions occur in Fenton’s reactions which

are [90]:

63
Fe+2 + HO2 • → Fe+3 + HO−2 (3.15)

Fe+3 + HO2 • → Fe+2 + O2 + H + (3.16)

OH• + H2O2 → H2O + HO2• (3.17)

From reaction (3.17), H2O2 can work as an OH• scavenger or as an initiator as is

seen in reaction (3.12). Finally hydroxyl radical reacts with ferrous ions forming

hydroxyl anion and ferric ions.

This is the termination step which is shown in the following reaction [27]:

OH• + Fe+2 → OH− + Fe +3 (chain termination) (3.18)

The overall Fenton chemistry can be simplified by accounting for the dissociation

water this is according to the following reaction [91]

2Fe+2 + H2O2 + 2H+ → 2Fe+3 + 2H2O (3.19)

Equation (3.19) shows that the presence of H+ is necessary to decompose H2O2.

This gives an indication of the need for an acidic environment to generate

maximum quantity of hydroxyl radicals that will oxidize the contaminants. Incase

complete oxidation occurs; contaminants decompose into water, carbon dioxide

and some non toxic inorganic salts [92].

Hydroxyl radicals oxidize the organic compounds (RH) resulting a production of

organic radicals (R•), which are very reactive and can be further oxidized [93, 94]

RH + OH• → H2O + R• → (chain propagation) (3.20)

Where R refers to any organic contaminant

R• refers to organic free radicals

This reaction is chain propagation initiating a radical chain oxidation which can

be further oxidized [95, 96]:

R• + H2O2 → ROH + OH• (3.21)

64
R• + O2 → ROO• (3.22)

The organic free radicals produced in reaction (3.20) may then be oxidized,

reduced, or demniralized according to the following reactions [97]

R• + Fe+3 oxidation → R+ + Fe+2 (oxidation) (3.23)

R• + Fe+2 → R − + Fe+3 (reduction) (3.24)

2R•- → R–R (dimerization) (3.25)

Fenton’s reagent can accomplish both chemical oxidation as well as coagulation

treatment. Adjusting the pH to a range of 5-7 will result in precipitation of

dissolved ferric particle. Precipitated ferric particle solids will combine to form

flocs that will help remove the dissolved solids. As a result, Fenton’s method can

achieve both chemical oxidation as well as coagulation treatment. Fenton’s

reagent is known to have different treatment functions depending on the

H2O2/FeSO4 ratio. The ratio can determine the degree of oxidation to coagulation.

In Fenton’s reaction chemical oxidation effect is dominant when the amount of

hydrogen peroxide exceeds the amount of ferrous salt (ratio above 2).While, the

coagulation effect is dominant when the two amounts are reversed (ratio below

1/5) [98]. The aim of implementing the chemical oxidation process is destruction

of contaminants and not to physically separate the contaminants. Because of that,

it is very significant to select the accurate ratio to guarantee destruction of

contaminant [99].

Other important parameters in Fenton’s reaction that must be studied are pH,

temperature, ferrous salt concentration and reaction time [99-103]. From the

overall reaction of Fenton’s chemistry, the pH can affect the system effectiveness

as acidic media is required for the reaction to occur. The best pH value falls in the

65
range of 3 to 5 [101]. Once Fenton’s reactions reach to completion, ferric

particles in the treated effluent enable coagulation treatment easily by neutralizing

the pH to 7. At this ferric ion converts into insoluble solid that precipitate and

easily removed by sedimentation basin [98]. Finally, the treated effluent is sent to

the biological treatment to achieve the desirable quality of treatment [100].

Ferrous sulfate concentration can contribute in Fenton’s reaction in two main

ways: oxidation as well as coagulation treatment. When the ferrous concentration

increases, more coagulation treatment occurs [102].

Another parameter that affects the reaction efficiency is the temperature. Fenton’s

reaction is an exothermic reaction and any increase in the temperature will result

of an increase of exothermic reaction rate. However, temperature increase causes

decomposition of hydrogen peroxide that reduces the efficiency of the process

[103].

The last parameter is the reaction time. It is essential to ensure enough residence

time to allow oxidation to occur [101].

3.3.1. Effect of pH in Fenton’s Reagent on the Removal of COD

The pH was adjusted to 1.5, 2.5, and 3.5, and 4.5 using 98wt% sulfuric acid.

Ferrous sulfate catalyst 6.6 mMole/l was added to the spent caustic solution as

solid and continuous mixing was applied to totally dissolve the catalyst.

Hydrogen peroxide 19.541 mMole was then dosed into the reactor. The

temperature was controlled and maintained around 45-65 ℃. 60 minutes reaction

time was fixed. Then the treated sample was neutralized to a pH value around 8-9

by a 5.0 M sodium hydroxide. A neutralized sample is then withdrawn and

66
centrifuged in order to separate the iron floc from the treated liquid; the liquid is

then decanted and analyzed for COD and sulfide.

The pH value considered to be a major factor in Fenton’s reaction and can

influence the process efficiency [45]. It can be observed the overall reaction of

Fenton’s chemistry in equation (3.12), the amount of HO• generated by the

Fenton process is affected by the pH. Acidic media is required for the reaction to

occur to produce the hydroxyl radicals as in equation (3.19).

It was noticed that the sample get clear when applying the oxidant reagent alone ,

however applying the Fenton’s reagent to sample result in a slight turbidity due to

the presence of traces of iron catalyst.

The results show that the optimum pH tested was found to be pH 2.5 with a

maximum conversion about 95.6% as in Figure 22.

100

98

96
95.58
94 94.79
COD % removal

94.067
92

90

88 89.42

86

84

82

80
pH=1.5 pH=2.5 pH=3.5 pH=4.5
pH

Figure 22 : Effect of pH on the COD removal

67
At operating pH >2.5 the decomposition rate decreases because of the decrease of

the free iron species in the solution, probably due to the formation of Fe (II)

complexes with the buffer inhibiting the formation of free radicals and also due to

the precipitation of ferric oxyhydroxides [104, 105] which inhibit the regeneration

of ferrous ions as in equation (3.26) and (3.27). Also, the oxidation potential of

HO• radical is known to decrease with an increase in the pH [106]

Fe+2 + H2O2 → Fe+3 + HO• + HO− (3.26)

Fe+2 + HO• → Fe+3 + HO− (3.27)

At lower pH (pH<2.5) the formation of (Fe(II) H2O) +2 occurs, which reacts more

slowly with hydrogen peroxide, therefore, generates less amount of hydroxyl

radicals that lead to reducing the degradation efficiency [107]. Moreover, the

scavenging effect of hydroxyl radicals by hydrogen ions becomes important at a

very low pH [108]. And the reaction of Fe+3 with hydrogen peroxide is inhibited

[109].

3.3.2. Effect of Ferrous Sulfate Concentrations on COD Removal

The main objective of ferrous sulfate catalyst is to release hydroxyl radicals from

hydrogen peroxide. Because of that it is essential to estimate the best ferrous

sulfate concentration that will generate the highest amount of hydroxyl radicals.

It was observed that after the addition of ferrous iron to the sample the color of

the sample started changing while adjusting the pH value due to the reactions

happening. It was also observed that a precipitate of iron was formed after

quenching the reaction with sodium hydroxide.

68
The effect of ferrous sulfate concentration on COD removal was studied. For all

samples, 97mMol/l of hydrogen peroxide is fixed and ferrous sulfate added to

spend caustic was varied (2.63, 1.32, 0.88, 0.66, and 0.13) mMole/l. As shown in

Figure 23, COD % removal decreases as the concentration of ferrous sulfate

decrease since ferrous ions will activate hydroxyl radicals. The maximum COD

removal is around 87.5 % at ferrous sulfate concentration of 2.63 mMol/l and

pH=2.5. The decrease in COD removal happens due to the scavenging effect of

ferrous ion as shown in equation (3.28). Ferrous ions consume hydroxyl radicals

to form HO2• radicals that ends with several chain reactions as in equation (3.15-

3.17). This results in lowering the COD removal [27].

Fe+3 + HO2• → Fe+2 + O2 + H+ (3.28)

pH=2.5
100
pH=1.5
98
96
COD % reemoval

94
92
90
88
86
84
82
80
0 0.5 1 1.5 2 2.5 3
FeSO4 mMole

Figure 23 : Effect of ferrous sulfate concentration on COD % removal

69
3.3.3. Effect of Hydrogen Peroxide to Ferrous Sulfate Ratio on COD

Removal

It is critical to find the best ratio of hydrogen peroxide to ferrous sulfate that will

generate the highest amount of hydroxyl radicals. Hydroxyl radicals oxidize

contaminants in spent caustic which result in lower COD [45]. As COD removal

increases, more hydroxyl radicals are being generated and vise versa [45].

Fenton’s reagent is known to have different treatment functions, depending on the

H2O2/FeSO4 ratio. There are three kinds of treatment that can be achieved

according to the ratio:

1. Physical separation as chemical coagulation: When the amount of Fe+2

employed exceeds that of H2O2. Coagulation is dominant rather than oxidation

which is undesirable since the aim is oxidation treatment [45]. Also, ferrous

ions will compete with contaminants to react with hydroxyl radicals [98].

Ferrous ions will terminate hydroxyl radicals as shown in reaction (3.29). This

reaction can convert ferrous ions from a catalyst to a reactant. This leads to

lower hydroxyl radical’s utilized for the oxidation of contaminants.

OH• + Fe+2 → OH− + Fe+3 (3.29)

2. Chemical oxidation (high ratio): When the amount of hydrogen peroxide is

much higher than ferrous ions, oxidation treatment is dominant [98]. This case

is desirable because the aim of applying Fenton’s reaction is the oxidation of

contaminants rather than physical separation. However, the issue with this

ratio is competition of hydrogen peroxide and contaminants to react with

hydroxyl radicals. Hydroxyl radicals tend to react with hydrogen peroxide

instead of reacting with contaminants generating HO2• as shown in reaction

70
 (3.32). Moreover, HO2• reacts with ferrous or ferric ions as shown in reactions

(3.30) and (3.31). This will end with decreasing the removal of COD and loss

in efficiency will occur.

Fe+2 + HO2• → Fe +3 + HO−2 (3.30)

Fe +3 + HO2• → Fe+2 + O2 + H+ (3.31)

OH• + H2O2 → H2O + HO2• (3.32)

3. Chemical oxidation (Medium ratio of [Fe+2]/[H2O2] ≅1): When the amount of

hydrogen peroxide to ferrous ions falls in between the previous two extremes.

At this range, hydroxyl radicals tend to react with contaminants instead

hydrogen peroxide or ferrous as shown in reaction (3.33). At this range,

ferrous ions react with hydrogen peroxide rather than reacting with hydroxyl

radicals and maximum amount of hydroxyl radicals are generated [98].

RH + OH• → H2O + R• (3.33)

Table 16: Effect of hydrogen peroxide to ferrous sulfate ratio on COD % removal

H2O2 FeSO4 FeSO4 H2O2 H2O2/FeSO4 pH=2.5 pH=1.5

(ml) (g) (mMole) (mMole) Ratio COD COD
(mg/l) (mg/l)
1 0.1 0.1 13.16 19.54 1.48 1029.5 1149.5
2 0.1 0.05 6.58 19.54 2.97 653 890
3 0.1 0.02 2.63 19.54 7.42 542 741
4 0.1 0.01 1.32 19.54 14.84 616.7 816
5 0.1 0.005 0.66 19.54 29.68 858.5 1103

The optimal ratios of chemicals in the Fenton process recommended in the

literature are the ratios H2O2/catalyst from 5:1 to 40:1 [110].

71
In the experiments, the selected ratio was of hydrogen peroxide to ferrous sulfate

(1.5:1), (3:1), (7:1), (15:1), and (30:1). As shown in Table 12.

100 pH=2.5
pH=1.5
98

96

94

92
COD % removal

90

88

86

84

82

80
0 5 10 15 20 25 30 35
H2O2/FeSO4

Figure 24 : Effect of hydrogen peroxide to ferrous sulfate ratio on % COD removal

Figure 24 shows the COD % removal for different hydrogen peroxide to ferrous

sulfate ratios for pH=1.5 and 2.5. At the beginning of the run, concentration of

ferrous ions in spent is high since it is all added at once while concentration of

hydrogen peroxide is low since it is dosed to the system. As a result, ferrous ions

consume hydroxyl radicals as in equation (3.29). The reaction proceeds, ferrous

ions concentration drops as more ferrous ions react with hydrogen peroxide and

hydrogen peroxide to ferrous ions ratio approaches optimum ratio. At this ratio

chemical oxidation will take place. In this case hydroxyl radicals tends to react

with contaminants as in equations (3.20 - 3.25). At pH=2.5, the maximum COD

72
removal of 96.4% is achieved at hydrogen peroxide to ferrous sulfate ratio of

(7:1) while the minimum COD removal is 94.3% at a ratio of (30:1). Furthermore,

at pH=1.5 the maximum COD removal of 95.1% is achieved at hydrogen

peroxide to ferrous sulfate ratio of (7:1) while the minimum COD removal is

92.6% at a ratio of (30:1)

3.3.4. Effect of Hydrogen Peroxide to COD ratio on Percentage COD

Removal

The optimum ratio of hydrogen peroxide to ferrous sulfate ratio was found,

hydrogen peroxide to spent caustic initial COD ratio is needs to be determined.

This ratio is essential in Fenton’s reaction because it verifies the amount of

hydrogen peroxide that should be used to carry the treatment of spent caustic. The

cost of treatment by Fenton’s process mainly depends on the cost of chemicals.

Chemicals used in Fenton’s reaction are hydrogen peroxide, ferrous sulfate,

sulfuric acid and sodium hydroxide. The cost of hydrogen peroxide is the most

expensive. So the running cost mainly depends on hydrogen peroxide to COD

ratio. Different hydrogen peroxide to COD ratios is tested to find out the required

ratio to achieve the desired treatment degree.

Table 1 show three experiments were done at pH=2.5 with different H2O2 to COD

ratio. Then the COD % removal was studied.

73
Table 17: Effect of hydrogen peroxide to COD ratio on % COD removal

H2O2 H2O2 FeSO4 FeSO4/ Initial Final COD H2O2 /COD

(ml) (g/l) g/l H2O2 COD COD % g/g

Ratio (mg/l) (mg/l) removal

0.1 0.66 0.4 7.4 15000 542 96.39 1.23

0.5 3.32 2 7.4 15000 1863 87.58 1.78

1 6.64 4 7.4 15000 2410 83.93 2.76

From Figure 25 it can be seen that as the hydrogen peroxide to COD ratio

increases, COD removal decrease. This is due to the competition of hydrogen

peroxide and contaminants to react with hydroxyl radicals. Hydroxyl radicals

react with hydrogen peroxide instead of reacting with contaminants as discussed

previously. This will decrease the removal of COD. The maximum tested COD

removal achieved was 96.4% with a ratio 1.23 H2O2 /COD (g/g) of and the lowest

tested COD removal was 83.9% at a ratio of 2.76 H2O2 /COD (g/g).

Maximum COD removal obtained is 542 mg/l which satisfy the desirable removal

to proceed to the biological treatment.

74
 100.00

98.00

96.00
1.23
94.00
COD % removal

92.00

90.00

88.00
1.78
86.00

84.00
2.76
82.00

80.00
H2O2/COD (g/g)

Figure 25 : Effect of hydrogen peroxide to COD ratio on % COD removal

75
CHAPTER 4:

4. CONCLUSIONS AND RECOMMENDATIONS

Different methods to treat sulfuric spent caustic have been suggested. Spent

caustic from ethylene plants has a relatively low COD content where it can be

treated by chemical treatment. However, solutions with higher COD values can be

more suitably treated by thermal treatment. Because the higher COD content

would require the consumption of great amounts of expensive reactants and high

energy cost. An efficient COD removal can be achieved by oxidation with

Fenton’s reagent. Which is a mixture of hydrogen peroxide and an iron catalyst

that is used to oxidize contaminants which results in the generation of highly

reactive hydroxyl radicals.

Usually ethylene plant spent caustic undergoes two treatment steps, chemical

treatment followed by biological treatment. The goal of chemical treatment is to

drop the concentration of contaminants to a level that biological treatment can

take place. The maximum contaminant’s concentration where biological treatment

can be applied, is COD less than 1,000 mg/l and sulfide 2 mg/l. Different

treatment processes were tested to check if the method can be applied to the

ethylene plant spent caustic treatment:

 Neutralization:

By Applying neutralization alone effect of pH and temperature on sulfide

removal was studied. The best removal percentage of sulfide was at a pH value

equal to 1 where 99.8 % of sulfides (9.9mg/l) were removed from solution. This

76
removal was achieved at T=60 ℃ . Moreover, the effect of pH on COD and

TDS % removal was studied. The average COD % removal after neutralization

to pH =7-8 for pH=1, 3 and 5 was about 85% while for pH=7and 8 the removal

was less than 80 %. Whereas the average removal of TDS was around 52 % for

pH= 1,3,5,7 and 8. The results show that the change in the pH as a function of

chemical addition had a very slight effect on TDS.

 Neutralization coupled with oxidation: classical oxidation

Effect of hydrogen peroxide concentration on COD % removal was studied. H2O2

interference with analytical procedures causes an increase in the COD value. This

is due to the reaction of dichromate ions and hydrogen peroxide in an acidified

solution. The interference was canceled by increasing the pH after the treatment

and centrifuging the samples solution. It was found that COD % removal

increases as the concentration of hydrogen peroxide increases due to the

generation of hydroxyl radicals. The maximum COD % removal was around 89%

at pH=2.5 and hydrogen peroxide concentration 0.1 ml. For the sulfide %

removal, it reached almost 100% in the treated samples.

 Neutralization coupled with Oxidation : Advanced Oxidation Process using

Fenton’s Reagent

The effect of different parameters (pH, ferrous sulfate concentrations, hydrogen

peroxide to ferrous sulfate ratio, and hydrogen peroxide to COD ratio ) on the

removal of COD were studied. It was found that:

77
o The optimum pH was found to be 2.5 with a maximum conversion

of 95.6% where as 19.541 mMole H2O2 and 6.6 mMole/l FeSO4

were fixed.

o The maximum COD removal was around 87.5 % at ferrous sulfate

concentration of 2.63 mMol/l and a pH value of 2.5. The decrease

in COD removal happens due to the scavenging effect of ferrous

ion that consume hydroxyl radicals to form HO2• hydroxyl radicals

resulting in lower COD removal

o Fenton’s reagent is known to have different treatment functions,

depending on the H2O2/FeSO4 ratio. At pH=2.5, the maximum

COD removal of 96.4 % was achieved at hydrogen peroxide to

ferrous sulfate ratio of (7:1).

o As the hydrogen peroxide to COD ratio increases, COD removal

decrease. This is due to the competition of hydrogen peroxide and

contaminants to react with hydroxyl radicals. The maximum tested

COD removal achieved was 96.4% with a ratio 1.23 H2O2 /COD

(g/g) at pH=2.5. Maximum COD removal obtained was 542 mg/l

which satisfy the desirable removal to proceed to the biological

treatment.

o In order to reach the discharge limit COD less than 1,000 mg/l and

sulfide 2 mg/l. it is recommended to use Fenton’s reagent. The best

removal was obtained 542 mg/l at pH=2.5 with 7.4 FeSO4 /H2O2

Ratio and 1.23 H2O2/COD (g/g).

78
CHAPTER 5:

5. FUTURE WORK

In order to further polish the treated spent caustic solution, biological treatment is

suggested. Chemical contaminants are broken down into simpler chemical units in

the oxidation step. These simpler chemicals are called "biodegradable species”

that can be degraded by the natural action of living micro-organisms. However a

great deal of technological challenges must be overcome this requires a high

performance biological treatment step that will eliminate a wide range of

pollutants. Further oxidation of the treated solution is done in anaerobic reactor

containing oxidizing bacteria. Biological treatment is considered as inexpensive

disposal and efficient method. Future studies should combine the chemical

processes with the biological processes to study the impact of the chemical

processes on the biological process.

79
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