N. M. Nasser

Investigation of the Demulsification Efficiency of Some Ethoxylated Polyalkylphenol Formaldehydes Based on Locally Obtained Materials to Resolve Water-in-Oil Emulsions

Fourteen ethoxylated polyalkylphenol formaldehyde surfactants were prepared from locally sourced raw materials. These surfactants were used as demulsifiers to resolve asphltenic crude oil emulsions. Different factors affecting demulsification efficiency such as water:oil ratios, surfactant concentration, surfactant molecular weight, ethylene oxide content, alkyl chain length, and asphaltene content were investigated. From the data obtained it was found that the demulsification efficiency increases by increasing the concentration, alkyl chain length and water content in the emulsion. Also it was found that the increase of asphaltene content in the crude oil impeded the demulsification efficiency. The effect of molecular weight was studied and it was found that the demulsification efficiency was controlled by an optimum range of molecular weight between 3640 to 3810 for the family of demulsifiers studied. Regarding the effect of ethylene oxide content in the demulsifier structure, it was found that the maximum demulsification efficiency was obtaind at 40 units ethylene oxide. The maximum demulsification efficiency was obtained by TND5 (m.wt. = 3800, eo = 40 units). With this demulsifier 100% water separation was exhibited after 35 minutes at 150 ppm demulsifier concentration and 50% w/o emulsion. The surface, interfacial tension, and hydrophilic lipophilic balance (HLB) of the invistigated demulsifers were studied. The obtained results justified that they are strongly related to the demulsification effeciency.

A New Family of Surfactants: Part I: Synthesis of Ethoxylated Monoalkyl Bisphenol and Their Investigation as Corrosion Inhibitiors

Twelve new ethoxylated mono alkyl bisphenol surfactants were prepared. These surfactants have a general formula as E(X) B(Y) M(R) wherein, the E(X) is the degree of ethylene oxide units, the B(Y) is the bisphenol which based on acetophenone (BAC), cyclohexanone (BCH), or acetone (BA) and R is the alkyl chain of fatty acids (decanoic, lauric, myristic, palmitic, stearic, oleic, linoleic, or linolinic). The chemical structures were confirmed using FTIR. The surface active properties for these surfactants were calculated using surface tension measurements. They were tested as corrosion inhibitors for carbon steel alloy in 2 M HCl solution the inhibition efficiency was evaluated using potensiostate Wenking 81 M. The efficiency of inhibitors was discussed on the light of their chemical structures such as alkyl chain length, degree of unsaturation, ethoxylation, bisphenol skeleton, and structure modification. From the data obtained it was found it was found that a strong relation between the surface active properties and the corrosion inhibition efficiency, also, the results clear that the corrosion inhibition efficiency increases with increasing the degree of unsaturation, ethoxylation, and alkyl chain length. Regarding to the bisphenol skeleton, it was noticed that the minimum inhibition efficiency was exhibited by bisphenol BCH, but the maximum efficiency was obtained by bisphenol BAC. As a result of these parameters, the 87.68% corrosion inhibition efficiency was obtained by inhibitor E(43) BCHMLL and 93.32% efficiency was exhibited by E(43) BACMLL.

Corrosion Inhibition Efficiency in Relation to Micellar Interaction Parameters of Cationic/Nonionic Surfactant Mixtures for Carbon Steel Pipelines in 1 M HCl Solution

The effect of different nine molar mixed ratios of didecyl dimethyl ammonium chloride as a cationic surfactant and nonyl phenol ethoxylate (e.o. = 9) as a nonionic surfactant, on the inhibition behavior of carbon steel have been examined using the weight loss and the potensiodynamic methods. The results show that these mixed cationic/nonionic surfactant mixtures (II to X) can be used to inhibit the corrosion of steel pipelines in the petroleum acid job. The surface active properties of the used surfactant mixtures were calculated using the surface tension measurements and the critical micelle concentration (CMC) values. The micellar interaction parameters of the investigated mixtures were calculated using the data of CMC. From the corrosion results it was found that, the maximum synergistic effect was obtained by the mixtures VIII (30%C + 70%N) and IV (70%C + 30%N). They exhibited inhibition efficiency expressed by the rate of corrosion as 5.15 and 1.53 miles per year respectively, at 400 ppm. The positive synergistic behavior of these mixtures pronounced the better results than which obtained by the individual inhibitors (cationic or nonionic alone). At the same time the maximum micellar interaction parameter was obtained by the mixtures VIII and IV (−1.85 and −1.80, respectively). These results justified the strong relationship between the corrosion inhibition efficiency and the micellar interaction parameters of the mixed surfactants which used as an organic corrosion inhibitors.

Some Cutting Oil Formulations Based on Local Prepared Emulsifiers Part I: Preparation of Some Emulsifiers Based on Local Raw Materials to Stabilize Cutting Oil Emulsions

The first main target of this work is to synthesis some emulsifiers from local raw materials used for cutting oil formulations. Seventeen emulsifiers (15 nonionic and 2 anionic) were prepared from locally available materials such as linear alkyl benzene sulfonic acid (LABSA), glycerol, polyethylene glycol, and maleic anhydride. Their chemical structures were confirmed using FTIR. The surface tension for the emulsifiers was measured at 25°C, and the surface and thermodynamic properties were calculated based on the surface tension parameters. The formulations of cutting oil fluids were prepared using these emulsifiers. The second target is to investigate the stability of soluble oil blends and emulsion stability of soluble oil in water. The results are discussed in the light of surface‐active properties and chemical structure of emulsifiers.

Demulsification Efficiency of Some New Demulsifiers Based on 1,3,5-Triethanolhexahydro-1,3,5-triazine

This study mainly concentrates on the synthesis of three novel demulsifiers and the investigation of their demulsification efficiency. The demulsifiers were derived from 1,3,5-triethanolhexahydro-1,3,5-triazine, which was prepared by the reaction of monoethanol amine with formaldehyde. The 1,3,5-triethanolhexahydro-1,3,5-triazine was ethoxylated by introducing 20 units of ethylene oxide and then esterified at different molar ratios with oleic acid (1, 2, and 3) to give three demulsifiers, namely, E20TO, E20TO2, and E20TO3. The chemical structures of the prepared demulsifiers were confirmed by 1H NMR and FTIR spectrum. The demulsification efficiency of these demulsifiers was tested on the natural water-in-oil (w/o) emulsions (50% water content). From the obtained results, it has been found that the investigated demulsifiers have a great potential to break the w/o emulsions. The trioleat ester (E20TO3) exhibited the maximum demulsification efficiency (96%) after 120 minutes at 55°C.

Surface Active and Thermodynamic Properties in Relation to the Demulsification Efficiency for Some Ethoxylated Derivatives of Alkyldiamines and Polyalkylenepolyamines

In this work, nine monostearic esters of ethoxylated dialkyle-amine (group I) and ethoxylated polyalkylenepolyamine (group II) nonionic surfactants were prepared and characterized by FTIR spectroscopy and nitrogen content. The 1,4-diaminobutane (DAB), 1,6 diamino hexane (DAH), 1,8-diamino-octane (DAO), diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) were ethoxylated at 50, 100, 150 ethylene oxide units individually. The ethoxylated products of (group I) reacted with stearic acid to give the monostearate products. The surface tension of the prepared compounds were measured at 25°C and 60°C. The thermodynamic parameters of micellization and adsorption were also calculated. The surface active properties, such as critical micelle concentration (CMC), maximum surface excess concentration (Γmax), effectiveness of surface tension reduction (πcmc), and minimum area per molecule at the aqueous solution-air interface (Amin), have been calculated. The surface active and thermodynamic properties of the prepared compounds were correlated to their chemical structure. It was found that CMC decreases when increasing the molecular weight of polyethylene oxide units. Furthermore, the data show that the synthesized surfactants favor adsorption than micellization, so that they can be used as demulsifiers for waxy crude oil emulsion (BSW 18%). In this respect, the demulsification test was carried out and the results of demulsification efficiency were correlated to the chemical composition of the investigated compounds. Some factors that affect the demulsification efficiency were also considered such HLB, concentration and time. The maximum demulsification efficiency (100%) was obtained by DAOE150-M and TEPAE150 at 60 and 45 minutes (300 ppm), respectively.

Synthesis of Some Oil Spill Dispersants From Locally Alkyl Benzene and Evaluating Their Dispersion Efficiency and Toxicity

Seven surface-active agents used as oil spill dispersants were prepared based on linear alkyl benzene-N-hydroxyl ethyl sulfonamide. Five of them are nonionic and the other two are ionic. These surfactants were prepared from locally raw materials. Their chemical structure and surface-active properties were investigated using the FT-IR, surface tension, and interfacial tension measurements. The efficiency of these dispersants was compared with a commercial used dispersant from Dasic Company. The toxicity test was carried out using aquatic animal (Modiolus adriaticus). The animal was exposed to these dispersants for 120 h at different dispersant to oil ratio. From the obtained results it was found that, the percentage of mortality of mussels after 1-h exposure from the start of the tests equalized zero. It varied with passing time up to 120 h, at which the mortality rate became 50%.

Demulsification Efficiency of Some New Stearate Esters of Ethoxylated and Propoxylated 1,8-Diamino-Octane for Water in Crude Oil Emulsions

In this work, eight demulsifiers were prepared from 1,8-diamino-octane (DAO). The DAO was ethoxylated or propoxylated up to 100 ethylene or propylene oxide units respectively. These alkoxylated products were esterified to mono, di, tri, and tetra stearate. The chemical structure was confirmed by FTIR and nitrogen content. The surface active parameters of these surfactants were investigated on the basis of the surface tension measurements at 25°C and 60°C. These surfactants were tested as emulsion breakers (demulsifiers) against waxy crude oil emulsion (Water content (BSW) = 18%). From the obtained data, it was found that the prepared materials have surface active properties let them act as good demulsifiers. The maximum demulsification efficiency (100%) was obtained by DAOE100-1 at 400 ppm[30 min], the mixture of (DAOE100-1 + DAOP100-2) in ratio [3:1] at 400 ppm and (DAOE100-2 + DAOP100-1) in ratio [1:3] at 400 ppm at temperature 60°C the time taken for complete water separation was 15 and 9 minutes. for these mixtures, respectively. The flow properties of the emulsion with and without the demulsifier were investigated. The obtained results showed that the demulsifiers used enhance the dynamic viscosity and yield value (τB). The viscosity was reduced from 10.5 for the untreated crude oil to 3.58 for the treated crude oil at concentration 100 ppm and a temperature of 60°C, meanwhile the τB was reduced from 0.054 for crude oil to 0.013 for the treated sample at the same condition.

Investigation Factors Affecting Cutting Oil Formulations Prepared by Emulsifiers Based on Linear Alkyl Benzene and Oleic Acid‐Maleic Anhydride Esters

Seven emulsifiers based on linear alkyl benzene and five others based on oleic acid maleic anhydride esters were prepared previously (Al‐Sabagh, A.M., Maysour, N.E., Nasser, N.M., and Srour, M.R. (2006) J. Dispersion Sci. Technol., 27 (2): 239–250). The prepared emulsifier package contains four components: synthesized surfactant, oleic acid, diethanol amine, and solvents. These four components and the base paraffin oil were used in all prepared different soluble oil formulations. The different percentages of these components are incorporated to optimize the stability of emulsifier systems. The evaluation was drawn in five factors: oil stability, emulsion stability, pH, corrosion inhibition, and extreme pressure performance tests. The obtained results shows that the formulations which prepared by ABPG(4)S and ABE(9)S exhibited a good performance results. The cutting oil formulations, which based on dodecyl benzene sulfonic acid pronounced anticorrosion properties (0/0–0) comparing with the formulations, which based on maleic anhydride esters (0/1–1). The wear scar diameter performance test was carried out for all the prepared cutting oil formulations. The obtained data shows that the ABE(9)S, ABPE(4)S and SABS exhibited scar diameters; 0.71, 0.74, and 0.75 mm, respectively. Meanwhile, the scar diameter of the currently used cutting formulation exhibited 0.76 mm. This means that these formulations can be used at high extreme pressure machines.

Investigation of Electro and Quantum Chemical Properties of Some Novel Cationic Surfactants Based on 1,3,5-Triethanolhexahydro-1,3,5-Triazine as Corrosion Inhibitors for Carbon Steel in Hydrochloric Acid

Three novel cationic surfactants incorporated with 1,3,5-triethanolhexahydro-1,3,5-triazine moiety were prepared and characterized. The inhibition efficiency of the prepared surfactants toward the carbon steel in 1 M HCl solution was investigated by weight loss, electrochemical polarization, and electrochemical impedance spectroscopy techniques. The maximum obtained efficiency was exhibited by N-dodecyl-1,3,5 tris (2-Hydroxypropane)1,3,5 triazinyl N-dodecylammonium bromide (DODT) against the three used techniques. The efficiencies were 97.0%, 94.4%, and 91.07%, respectively. The surface active properties for these surfactants were investigated. The quantum chemical parameters were also calculated. The data was discussed in light of surface active, corrosion inhibition, and quantum chemical properties to characterize the adsorption mechanism.