Sulfonation Reaction for the Synthesis of Anionic ... - UTPedia

Anionic surfactants are widely used in detergent products because of their ability to reduce the surface tension between oil and water. The amount of surfactant adsorption can be minimized as a result of repulsion between anionic surfactants and sandstones. Anionic surfactants are produced by combining SO3 with fatty alcohols, increasing the performance of the surfactants.

Sodium bisulfite reacts together with methyl chloride and fatty alcohols to produce sulfonate anionic surfactants. The title of this final year report is "Sulfonation Reaction for the Synthesis of Anionic Surfactants for EOR Application". The author also wishes to express his sincere gratitude to Associate Professor Dr Isa M Tan, supervisor for the author's Final Year Project for his dedication, support and enthusiasm which guided the author to complete his work on time.

Gratitude also extends to all employees of Universiti Teknologi PETRONAS, especially the lab technician/assistant, for their commitment and support. Finally, the author would like to thank everyone who has been directly or indirectly involved in this research.

INTRODUCTION

Background of study
Problem Statement
Objectives and scope of study
Feasibility of the Project within Scope and Time Frame

The yield of sulfonation will be analyzed, important data will be taken and the formulation will be achieved when all the parameters to optimize the yield of the sulfonate product have been identified. However, uncontrolled temperature can cause by-products to form or black solutions to form. The factors affecting the efficiency of the sulfonation reaction of sodium bisulfite with nonionic surfactants are unknown.

The main objective for this thesis is to investigate the reaction kinetics of the sulfonation process using sodium bisulfite (NaHSO3) with nonionic surfactants. Synthesis parameter such as reaction temperature, addition of catalyst and mole ratio of reactants will be manipulated to determine the concentration of anionic sulfonate surfactants produced in the reaction of step 2. The first part for the January 2013 semester, the author will focus on the proposal of the project, selection of the project title and literature review based on the project topic which is "Sulfonation Reaction for Synthesis of Anionic Surfactants for EOR Application".

Meanwhile, the second part of this project, in the May 2013 semester, will focus on the collection and analysis of experimental data. To ensure that this project achieves its objectives within the constraints, the project is executed according to plan during all phases of the project.

LITERATURE REVIEW

Principle of Enhanced Oil Recovery (EOR)
Surfactants Sulfonate
Sulfonation Reaction
Two Phase Titration

The M value can be made smaller by lowering the viscosity of the oil and/or increasing the viscosity of the displacement fluid, decreasing the permeability of the oil and at the same time increasing the permeability of the displacement fluid. Where ν is the Darcy velocity of the displacing fluid, µ is the viscosity of displaced fluid, σ is the interfacial tension between displaced fluid and displacing fluid, k is the effective permeability of displacing fluid, is the pressure gradient. Sulfonation generally refers to the addition of sulfur trioxide, SO3 to organic compounds to produce sulfate compound.

Failure to control the temperature reaction will lead to by-product formation. At present, researcher have developed some of the sulfonate reagents or donors to reduce SO3 reactivity during the sulfonation process for safety reasons. Referring to one of the Berger literature [9], several catalysts such as H2SO4, methanesulfonic acid, sulforauric acid and other strong acid are able to catalyze the reaction, reduce the reaction temperature and improve the yield of the final product.

Referring to Ellis et al [13], a study of the bisulfite reaction with olefins with the production of an alkyl sulfonated from the reaction of bisulfite ions on olefinic double bonds. The concentration of the sulfonated product can be determined by the two-phase titration method.

Figure 2.0. Effect of mobility ratio on water flood recovery. S.M Farouq on the principle of EOR

METHODOLOGY

Research Methods
Project Activities

Detailed Project Activities
Chemicals Reagent

Preparation of Chemicals

Non-ionic Surfactants
Mixed Indicator solution
Two Phase Titration

Research Key Milestones
FYP II Gantt’s Chart

Mixed indicator solution is prepared by mixing 20 ml of dimidium bromide, 200 ml of distilled water and 20 ml of 2.5 M sulfuric acid in 1 liter. Preparation for the titration process of the sulfonate anionic surfactants followed the procedure reported by Zelenev in his book [8]. 25 ml of water, 5 ml of mixed indicator solution and 5 ml of chloroform are mixed together with the sample.

A drop of 0.004 M Hyamine 1622 is added until the endpoint of the titration is reached where the aqueous layer which is pink gradually turns gray. To meet the research objectives, the following process flow chart has been created to ensure that the project is completed on time. To collect all necessary data from past research to support the purpose of research and to provide sufficient information to conduct research.

Conduct a discovery-based experiment following a specific procedure and gather useful data by observing and testing samples. To gather all useful information, for example, about the procedure of the experiment, the use of the formula and the result obtained.

RESULT AND DISCUSSION

Data Gathering and Analysis

Experiment Variables
Preparation of Anionic Surfactants Sulfonate
Experiment Flow Chart

Experiment Results

Anionic Surfactants Reaction (Step 1)
Sulfonation Reaction of Non-ionic Surfactants (Step 2)
Sulfonation of Non-ionic Surfactants (Mole Ratio Effect)
Sulfonation of Non-ionic Surfactants (Catalyst Effect)
Sulfonation of Non-ionic Surfactants (Temperature Effect)

The nonionic surfactants for this research purpose were prepared by reacting the fatty acids, commercially known as Novel TDA-6 Ethoxylate, with potassium chloride, KCl and methalyl chloride. The reaction proceeds to step 2 reaction or known as the sulfonation reaction of nonionic surfactants using sodium bisulfite, NaHSO3 as sulfur trioxide, SO3 donors. The FTIR result for this reaction is shown in Figure Table 6, where the success of step 2 is followed by the development of the sulfonate peaks.

The result of the experiment for Part 4.2.3 to investigate the effect of mole ratio is shown in Figure 4.4. Based on the graph shown in Figure 4.4, the highest yield recorded after a 24-hour reaction is 50.85 percent at a 1.0:1.2 ratio of nonionic surfactants to NaHSO3. Based on the last experiment, the experiment was set up in a similar way using 1.0:1.2 ratios of nonionic surfactants and NaHSO3 configuration.

Based on the graph shown in Figure 4.5, the maximum yield recorded after a 24-hour reaction is 65.90 percent under the conditions after the addition of the Al(NO3)3 catalyst. The result of the experiment for Part 4.2.5 to investigate the effect of mole ratio is shown in Figure 4.6.

Figure 4.4. Reactants mole ratio effect results

Experiment Discussion

Overall Reaction Mechanism
Estimation of Anionic Surfactants Sulfonate Concentration
Reactant Mole Ratio Effect Experiment
Catalyst Effect Experiment
Temperature Effect Experiment

Based on Figure 4.6, the yield versus time result at different temperatures showed that the highest product yield was at the boiling point temperature condition or 82.5 degrees Celsius (356 K) with a yield of 65.91% as opposed to the lowest yield obtained at room temperature condition a value of 20.44. Desulfonation will hinder further reaction of sulfonation reaction in step 2, which may reduce the yield of the final product. This provides evidence for the presence of double bonds formed at the end of the step 1 reaction.

The reaction for step 2 starts by refluxing the final product from reaction step 1 with ethanol and water as solvents. Therefore, it is true that the sulfur trioxide group will be attached to the double bonds produced during step 1 reaction. Reaction size for the sulfonation process was estimated using two-step titration as recommended by Zelenez [8] by titrating 0.004 M Hyamine 1622 in a solution consisting of sulfonate anionic surfactants, mixed indicator, chloroform and solvents.

Based on observation, the reaction between Hyamine 1622 between the solutions is faster at the beginning and the last reaction before the bottom solution turns completely gray. To determine the effect of the mole ratio towards the formation of the final product, the reaction was carried out using a fixed temperature and the same concentration of anionic surfactants. Based on Ellis et al[13], it is preferable to react in the condition where the mole ratio is about 1:1.0 to 1:1.5 to avoid the large amount of excess bisulfite in minimizing the residual inorganic material in the final product.

To determine the effect of catalyst against the formation of the final product after 24 hours, according to Norton [14] the highest olefin conversion reaches. The minimum amount of energy required for the reaction to occur, known as the activation energy, for the reaction to proceed. Catalyst is known to provide an alternative pathway for the reaction by lowering the amount of activation energy.

In order to determine the effect of temperature on the formation of the final product with time, the experiment was carried out at standard room temperature, 40oC, 60oC and 82.5oC. The reaction for the Step 2 reactions is a first-order reaction based on the natural log concentration versus time plot in Figure 4.10, which was drawn from the results of an experiment using molar ratios of anionic surfactants to NaHSO3 of 1.0:1.2. On the other hand, the value of the rate constant increases with time, proving the Arrhenius theory, the higher the temperature, the more energy the molecules will absorb; more frequent collision for reaction.

Table 4.4. The best reactants mole ratio shown in highlighted row.

CONCLUSION AND RECOMENDATION

Conclusion

Users should make their own investigations to determine the suitability of the information for their particular purposes. CERCLA Hazardous Substances and Relevant RQs None of the chemicals in this material have an RQ. None of the chemicals in this product are listed as hazardous substances under the CWA.

None of the chemicals in this product are listed as priority contaminants under the CWA. None of the chemicals in this product are listed as toxic contaminants under the CWA. Toxicity of products of biodegradation: The products of degradation are less toxic than the product itself.

Recomendation