New Amphiphilic Tricationic Imidazolium and Pyridinium Ionic Liquids for Demulsification of Arabic Heavy Crude Oil Brine Emulsions.

Preparation of new green oilfield chemicals based on ionic liquids (ILs) having higher demulsification efficiency to solve the heavy crude oil brine water emulsions became a target in the petroleum research studies and industry. In the present work, the combination of pyridinium, imidazolium, and hydrophilic or hydrophobic moieties in the chemical structure of ILs has been investigated to improve the surface properties of ILs in both bulk solution and interfaces. Aminopyridine was quaternized with cetylbromide and condensed with glyoxal and 4-hydroxybenzaldehyde in acetic acid to prepare imidazolium-pyridinium bromide acetate ionic liquid (IPy-IL). The phenol group of IPy-IL was etherified with tetraethylene glycol to alter its amphiphilicity and synthesize new amphiphiles (AIPy-IL). Their chemical structure, thermal characteristics, and stabilities were characterized. Their aqueous solution performance in seawater was evaluated to investigate their surface activity, aggregation particle sizes, and surface charges. The demulsification performances of the prepared Arabic heavy crude oil seawater emulsions in the presence of different concentrations of IPy-IL and AIPy-IL were evaluated and proved by interfacial tension, particle size, and demulsification efficiencies at a temperature of 45 °C. The data concluded that AIPy-IL was an effective demulsifier for different crude oil seawater emulsion compositions at a low injection dose and temperature of 100 ppm and 45 °C, which were not report elsewhere.

Introduction

Petroleum crude oil/n class="Chemical">brine water emulsions were formed during the production of heavy and medium crude oil because of the presence of asphaltenes in their chemicals constituents.[1] These emulsions caused several serious problems during petroleum crude oil production, transportation, and refining processes such as corrosion, pump failure, higher petroleum crude oil viscosity, formation of sludge and poisoning of the petroleum refining catalysts.[2] Chemical demulsification is considered the best method among thermal, electrical, biological, physical, and mechanical methods that were used to solve the formation of the petroleum crude oil emulsions.[3] Moreover, the chemicals used to inhibit the formation of petroleum crude oil/brine water emulsions have been considered to be injected in the petroleum crude oil reservoir to prevent the formation of petroleum emulsions.[4] The on site recovery of heavy crude oil affects the injection of chemicals preventing emulsion formation due to the use of steam, caustic injection or combustion processes increased the formation of more viscous crude oil/water emulsions included clay.[5] The most stable crude oil emulsions are based on water-in-oil (W/O) or multiple emulsions such as water-in-oil-in-water (W/O/W) or oil-in-water-in-oil (O/W/O types.[1] There are different chemicals that were used as demulsifiers for different types of crude oil/brine water emulsions. Polymeric surfactant mixtures and dendrimers were widely used as chemical demulsifiers to solve several petroleum crude oil emulsions.[6,7] The hydrophile–lipophile balance (HLB), molecular weights, solubility, and thermal stability of the polymeric surfactants are important parameters to formulate the polymeric surfactant mixtures to solve different types of petroleum crude oil emulsions.[6] Nanomaterials have also acquired considerable interest on the lab scale as chemical demulsifiers to increase the efficiency of the traditional monomeric and polymeric surfactants.[8−11] The designing of cost-effective preparation method with higher yield, regeneration process of nanomaterials and their effects on the environment ecosystem are still under consideration to apply as oil-field demulsifier chemicals. Recently, thermally stable and structure-flexible ionic liquids (ILs) have demonstrated great potential for chemical demulsification of petroleum crude oil emulsions.[12−15] Their structures affect their demulsification efficiencies and are tuned by playing with the anions and cations to obtain the desired properties.[13] Amphiphilic ILs (AILs) are new class of green surfactants that can be tailored for application in the petroleum oilfield to alter the water wettability, surface tension, and crude oil/water interfacial tension (IFT) because of their higher thermal stability, nonflammability, lower toxicity, and vapor pressure.[16−18] AILs solve the chemical demulsification problems of petroleum crude oil emulsions such as longer demulsification time, chemical demulsifier mixtures, higher injection doses, and higher demulsification temperature occurred from applying ILs.[19−21] In this respect, one of the objectives of the present work is to design new AILs to be applied as single chemicals to demulsify the petroleum crude oil/water emulsion at lower temperature and injection dose.

The chemical structures of cations and anions and lengths of alkyl chains of AILs play an important role in the outcome of the previous studies that were conducted to improve their efficiency as an effective chemical demulsifier.[14,15,20−24] The longer alkyl chains of cations and hydrophobic anions improve the demulsification performance and can act as AIL chemical demulsifiers.[22,23] The amphiphilic n class="Chemical">imidazolium ILs (AIILs) substituted with longer alkyl chains (ranged from C10–C14) combined with Cl, PF6 and bis(trifluoromethanesulfonyl) imide (NTf2) anions were used to demulsify the petroleum crude oil emulsions.[23] It is reported that the IILs contain C14 alkyl chains and NTf2 anions reduced the IFT of the petroleum crude oil/water emulsions, and they were more efficient demulsifiers.[23] Moreover, it is also reported that either AIILs or amphiphilic pyridinium ILs (AP–ILs) were designed to be not only able to tolerate the harsh reservoir salinity conditions but also to adsorb at oil/brine water interfaces to demulsify the petroleum crude oil emulsions.[25−27] The incorporation of aromatic moieties in the chemical structure of AIILs improves their ability to reduce IFT of the crude oil/AIIL.[28] In this work, our aims extended to design new combined imidazolium and pyridinium cations containing aromatic, long chain alkyl and oxyethylene moieties to improve the amphiphilicity and efficiency of ILs to act as demulsifiers for petroleum crude oil/brine water emulsions. The scheme of this work is based on quaternization of 4-aminopyridine (4-AP) with dodecyl bromide followed by condensation with glyoxal (GX) and p-hydroxybenzaldehyde (PHB) in acetic acid solution to prepare imidazolium–pyridinium ILs (IPy-ILs) containing dodecyl and aromatic phenolic moieties as the tail. The phenolic group of IPy-IL was ethoxylated with tetraethylene glycol (TEG) to improve its amphiphilicity and to produce amphiphilic IL (AIPy-IL), which combined both dipoles of imidazolium and pyridinium cations via Br– and CH3COO– anions. The surface activity and IFT measurements of both IPy-IL and AIPy-IL were conducted in seawater and heavy crude oil emulsion. The application of both the prepared IPy-IL and AIPy-IL as demulsifiers for W/O emulsion of Arabic crude oil at lower concentration is another objective of the present work.

Experimental Section

Materials

Glyoxal monohydrate, acetic acid, 4-hydoxybenzaldehyde (HBA), tetraethylene glycol (TEG), β,β-dichlorodiethyl ether (DCDE), N-N-dimethylformamide (DMF), and sodium hydroxide were purchased from Sigma-Aldrich chemicals Co. and used without further purification. Xylene (mixture of isomers) and ethanol (99.9%) were obtained from Sigma-Aldrich (St. Louis, MO, USA). Arabic heavy crude oil was supplied from Aramco Co., Riyadh refinery unit. The specifications of Arabic heavy crude oil are listed in Table . Seawater was collected from Arabian Gulf at the Dammam coast with salinity 40 practical salinity units (psu; g/L).

Table 1

Arabian Heavy Crude Oil Characteristics

test	results
API gravity	20.8
specific gravity 60/60 (F)	0.929
wax content, (wt %)	2.3
asphaltene content, (wt %)	8.3
heteroatoms (w/w %)	6.5
aromatic carbon (mol %)	49.0
aromatic hydrogen (mol %)	7.81
saturates (w %)	16.3
aromatics (w %)	25.3
resins (w %)	48.1

Synthesis of Demulsifiers

Dipyridinium imidazolium IL was prepared using quaternized aminopyridine, glyoxal, and p-hydroxybenzaldehyde. The product was then etherified using TEG and β,β-DCDE to obtain amphiphilic ethoxylated dipyridinium imidazolium IL.

Preparation of Dipyridinium Imidazolium IL

Quaternized amino pyridine was prepared in previous work[29] as follows: A-AP (0.01 mol, 3.17 g) was dissolved in 20 mL of acetic acid aqueous solution. Aldehyde solution was prepared by dissolving glyoxal monohydrate (5 mmol, 0.38 g) and HBA (0.005 mol; 0.61 g) in 20 mL of aqueous acetic acid. The pH of the reaction mixture was adjusted to 5. Aldehyde solution was added one time to amine solution under vigorous stirring and heated at 60 °C for 5 h. The reaction mixture was purified by washing several times with diethyl ether to obtain dipyridinum imidazolium IL (IPy-IL).

Etherification of the Prepared IL (AIPy-IL)

IPy-IL (2 mmol, 1.52 g) was mixed with TEG (2 mmol, 0.286 g), DCDE (2 mmol, 0.286 g), and NaOH pellets (4 mmol, 0.16 g) and was dissolved in xylene (20 mL) and refluxed for 6 h under vigorous stirring. The reaction mixture was filtrated by applying heat to separate the NaCl byproduct. The final product (AIPy-IL) was obtained by distillation from xylene using a rotary evaporator under reduced pressure as a brown oily product.

Characterizations of the Prepared ILs

The structures of the prepared ILs were investigated with 1H and n class="Chemical">13C NMR (Bruker AVANCE DRX-400) using DMSO-d6 as a solvent. FT-IR spectra were recorded using a Nicolet FT-IR spectrophotometer in the wavenumber range of 4000–400 cm–1. Thermal degradation stability of IPy-IL and AIPy-IL was evaluated from thermogravimetric analysis (TGA; TGA-50 SHIMADZU) using N2 at a heating rate of 10 °C.min–1. Thermal analysis was determined by DSC (Shimadzu DTG-60 M) with the heating rate of 10 °C min–1. The surface activities of the prepared ILs were studied using a drop shape analyzer (DSA-100) by preparing different concentrations of ILs in aqueous solution. Also, the IFT between Arabian heavy crude oil and sea water was determined. The micelle size and charge of the prepared amphiphilic ILs in aqueous solutions was studied using dynamic light scattering (DLS; Zetasizer Nano ZS, Malvern Instrument Ltd., Malvern, UK) at ambient temperature. The size of the prepared emulsion with time after the addition of demulsifiers was noticed using a Fluorescent Optical microscope (Olympus BX-51 microscope attached with a 100 W mercury lamp). To determine the relative solubility number (RSN), 1 g of IL was dissolved in toluene/dioxane solution and titrated against deionized water. The number of DW mills required to reach a cloud point of a clear solution is considered as the RSN value.

Water/Crude Oil Emulsion Preparation

Different calculated amounts of sea water were added to Arabian heavy crude oil in a 500 mL beaker gradually under homogenization with a rate of 5000 rpm for 30 min at 25 °C to prepare W/O emulsion with ratios of 50:50, 30:70, and 10:90. The emulsion type was confirmed to be water-in-oil using the drop dilution method.

Dehydration Study of the Prepared ILs

Demulsifiers with a concentration of 30 wt % dissolved in a xylene/ethanol mixture (75/25 vol %) were prepared. The demulsifier solution with a calculated volume was added to 25 mL cylinders containing the W/O emulsions and kept at 60 °C in a water bath. The demulsification process was monitored with time, and the separated water volumes were recorded until the steady state. A blank sample at the same demulsification conditions was considered. The dehydration efficiency (η %) was calculated using the relation η % = Vs/Ve; where Vs is the volume of demulsified water at a certain time and Ve is the total emulsified water volume.

Results and Discussion

The preparation method of IPy-IL and AIPy-IL is illustrated in Scheme and reported in the experimental section. Quaternization of 4-AP with alkyl bromide in different solvents such as DMF, dimethylsulfoxide (DMSO), and acetone was carried out to obtain high yields of quaternized nitrogen of pyridine without quaternization of the amine group.[29−31] In this respect, acetone was selected as the solvent to quaternize 4-AP with 1-bromotetradecane to form QCAP with yield 76%. The amine group of QCAP was condensed with aldehyde groups of GX and HBA in acetic acid solution to form IPy-IL with yield of 95%, as reported in the Experimental Section and Scheme . The OH phenol group of IPy-IL was reacted with TEG in the presence of DCDE and NaOH as a catalyst to obtain AIPy-IL with yield 85% (Scheme ). The purity and characterization of the prepared IPy-IL and AIPy-IL were examined from identification of their chemical structures, thermal characteristics, and stabilities.

Scheme 1

Synthesis Method of IPy-IL and AIPy-IL

Characterization of IPy-IL and AIPy-IL

The chemical structures of IPy-IL and n class="Chemical">AIPy-IL were confirmed by using FTIR, 1HNMR, and 13CNMR analyses, as shown in Figures –3a,b. The FTIR spectrum of IPy-IL (Figure a) shows the characteristics bands of pyridinium and imidazolium cations from the appearance of bands at 1620, 1593, and 1169 cm–1, which were attributed to C=C, (N)CH2, and C–N stretching vibrations, respectively. The bands at 3450, 3110, and 750 cm –1 in the spectrum of IPy-IL (Figure a) were referred to as phenol OH, =CH stretching, and =CH out-of-plane bending vibrations of the aromatic phenol group. The presence of the tetradecyl group in the chemical structure of IPy-IL (Figure a) was elucidated from the appearance of bands at 2750–2950, 1375–1450, and 950 cm–1, which were attributed to aliphatic CH stretching, bending, and (CH2)13 bending vibrations. All these bands were observed in the FTIR spectrum of AIPy-IL (Figure b) with broadness of the OH stretching vibration band at 3450 cm–1 and appearance of a new band at 1050 cm–1 of C–O stretching vibration. These bands confirm the etherification of the phenol group with ethoxy groups terminated with the alcoholic hydroxyl group (Scheme ).

Figure 1

FTIR spectra of (a) IPy-IL and (b) AIPy-IL.

Figure 3

13CNMR spectra of (a) IPy-IL and (b) AIPy-IL.

The chemical structures of IPy-IL and n class="Chemical">AIPy-IL were completely confirmed from their 1H NMR and 13C NMR spectra shown in Figures and 3a,b, respectively. The IPy-IL characteristic peaks and their integrations were marked with their analogous chemical structures and represented on its spectrum (Figures a and 3a). The presence of methyl of acetate anions and OH of the phenol group of IPy-IL was confirmed from the singlet peaks at chemical shifts 2.1 and 9.8 ppm, respectively. The disappearance of OH of the phenol group and appearance of a singlet peak at 4.6 ppm in the AIPy-IL spectrum (Figure b) as well as new peaks as the multiplet and triplet at 3.65 (OCH2) and 4.1 (Ph-OCH2) ppm confirm its ethoxylation. The CH=N+ peaks of imidazolium and pyridinium cations of IPy-IL and AIPy-IL were appeared in their spectra at 8.1–8.3 and 8.9 ppm, respectively (Figure a,b). The 13C NMR spectra of IPy-IL and AIPy-IL (Figure a,b) were used to confirm their C–CO, C–O, and C–N+ groups from the appearance of peaks at 21, 69–73, and 158–164 ppm, respectively. All peaks of tetradecyl, imidazolium, pyridinium, and phenyl groups of IPy-IL and AIPy-IL were correlated with their structures, as shown in Figure a.

Figure 2

1HNMR spectra of (a) IPy-IL and (b) AIPy-IL.

The thermal characteristics such as glass transition (Tg), crystallization (Tc), and melting (Tm) temperatures of n class="Chemical">IPy-IL and AIPy-IL were determined from their DSC thermograms and are shown in Figure a,b to elucidate that they acted as ILs and did not behave as normal salt. Both IPy-IL and AIPy-IL behave as ILs because they possess Tm values below 100 °C and because of the appearance of endothermic peaks at 87–89 and 70–71 °C, respectively (Figure a,b). The presence of aromatic phenol in the chemical structure of IPy-IL increases its rigidity and Tg value at −16.8 °C (Figure a) to be more than the Tg value of AIPy-IL determined at −53.9 °C (Figure b).[32] The incorporation of the polyethoxy group in the chemical structure of AIPy-IL increases its flexibility after ethoxylation of the OH phenol group of IPy-IL because of breaking of the hydrogen bond of phenol groups that increase IPy-IL rigidity and Tm and Tg values.[33] It was also noticed that AIPy-IL (Figure b) behaves thermally different from IPy-IL with the appearance of endothermic peak Tc at −13.4 °C (Figure b). The crystallization temperature of AIPy-IL elucidates its higher symmetry, effective charge distribution, and strong ion interactions.[34] While weak ion interactions (suppressing H bond) of IPy-IL reduces its crystallization lattice energy of its salts to be amorphous disappearance of its Tc (Figure a).[35] The appearance of one Tg and Tm peak for IPy-IL and AIPy-IL elucidates their higher purity.

Figure 4

DSC thermograms of (a) IPy-IL and (b) AIPy-IL.

The thermal stability of IPy-IL and n class="Chemical">AIPy-IL was determined from TGA–DTG thermograms shown in Figure a,b, respectively. The initial decomposition temperature (IDT) and maximum decomposition temperature (Tmax) remained residual at 750 °C, and Rs % of IPy-IL and AIPy-IL was determined from their TGA thermograms (Figure a,b). It was noticed that both IPy-IL and AIPy-IL did not lose water below 150 °C to confirm their purity after the purification procedure, as reported in the experimental section. The IPy-IL and AIPy-IL thermograms (Figure a,b) show appearance of two degradation steps to confirm the presence of two types of anions as acetate and bromide anions. The IDTs of IPy-IL and AIPy-IL are 200 and 285 °C, respectively, which confirm that the presence of acetate anion reduces their thermal stability due to protonation of acetate to acetic acid.[36] The first degradation step of IPy-IL (Figure a) was started from 200 to 330 °C, and it lost 40 wt %. The AIPy-IL’s (Figure b) first degradation step started from 285 to 350 °C, and it lost 35 wt % of its original weight. These data confirm that the presence of polyoxyethylene increases the thermal stability of AIPy-IL more than IPy-IL and lowers the protonation of acetate anions because of the disappearance of the phenol to phenoxy group.[36] The second degradation step of IPy-IL and AIPy-IL started at 330–420 and 350–450 °C, which lost 55 and 60 wt %, respectively. The Rs % of IPy-IL and AIPy-IL is 5 wt % (Figure a,b), which confirms the formation of cyclic carbon and nitrogen residue of thermally stable ILs.

Figure 5

TGA–DTG thermograms of (a) IPy-IL and (b) AIPy-IL.

Surface Activity of the Prepared ILs at the Seawater/Air and Crude Oil/Seawater Interfaces

It is very important to investigate the solution characteristics of the prepared amphiphiles in aqueous solution under harsh conditions, especially in seawater, because of their higher salinity, as reported in Table . In this respect, the n class="Chemical">RSN of IPy-IL and AIPy-IL was determined as reported in the experimental work and used to confirm their complete or partial solubility in seawater, which was in the range of 13–17 and above 17 mL in seawater, respectively.[37] The RSN values of IPy-IL and AIPy-IL are 20.6 and 17.3 mL in seawater, respectively, which elucidates that the solubility of the AIPy-IL in seawater was decreased with etherification of the phenol group with polyoxyethylene. It is well reported that the increasing ethoxylation length of amphiphiles increases their solubility in water.[38] It is well proposed that the presence of the oxyethylene unit in the chemical structure of AIPy-IL will decrease its solubility in seawater, increase its aggregation in bulk seawater solution, and increase its adsorption at interfaces. This speculation will be confirmed from the surface tension, hydrodynamic aggregation number, and zeta potential measurements as shown in Figures and 7. In this respect, the relation between seawater surface tension measurements (γ; mN/m) and different concentrations (ln c; mol/L) of IPy-IL and AIPy-IL was represented in Figure to determine their critical micelle concentrations (cmc; mol/L), slope (−∂γ/∂ ln c), and surface tension at cmc (γcmc; mN/m). These values were determined for both IPy-IL and AIPy-IL and are summarized in Table . The cmc data of AIPy-IL were lower than those determined for IPy-IL to confirm the lower solubility of AIPy-IL in seawater than IPy-IL, as confirmed from RSN data (Table ). These data elucidate that the phenol group of IPy-IL form hydrogen bonds with seawater, and the formation of the polyoxyethylene group leads to coiling of oxyethylene in seawater. The DLS data of IPy-IL and AIPy-IL at their cmc (Figure a,b) indicate that the coiling of oxyethylene in seawater increases the aggregation diameters and positive surface charges of AIPy-IL (Figure b and Table ). The coiling of the oxyethylene unit of AIPy-IL reduces its ability to reduce surface tension of seawater compared to IPy-IL, as elucidated from high γcmc and maximum reduction of surface tension of the seawater surface (Δγ = γwater – γcac; where γwater is the water surface tension at 25 °C). The coiling of the oxyethylene unit of AIPy-IL leads to increase in its surface charge to 49.7 mV when compared with zeta potential of IPy-IL at 7.05 mV (Figure a,b and Table ). Both IPy-IL and AIPy-IL form polydisperse aggregates at their cmc values, as elucidated from increasing their polydispersity index (PDI) values greater than 0.7 (Figure a,b). The low surface charge of IPy-IL at 7.05 mV and high surface charge of AIPy-IL at 49.7 mV indicated that IPy-IL and AIPy-IL molecules form neutral bilayers and multilayer micelles, as shown in Scheme a,b, respectively.[39]

Figure 6

Relation between seawater surface tension measurements and different concentrations of IPy-IL and AIPy-IL at 25 °C.

Figure 7

DLS data of (a) particle sizes of IPy-IL in seawater at its cmc, (b) zeta potential of IPy-IL in water using 1 mM KCl, (c) particle sizes of AIPy-IL in seawater at its cmc, and (d) zeta potential of AIPy-IL in water using 1 mM KCl at 25 °C.

Table 2

Surface Activity Parameters, RSN, and Zeta Potentials of IPy-IL and AIPy-IL at 25 °C

compound	cmc (mM)	(−∂γ/∂ ln c)T	γcmc (mN/m)	Δγ N.m–1	Γmax ×10 –6 (mol/m2)	Amin (nm2/molecule)	RSN	aggregation diameter (nm)	zeta potential (mv)
IPy-IL	0.657	5.943	36 ± 0.5	39.1 ± 0.5	2.473	0.067	20.6	1229	7.05 ± 0.1
AIPy-IL	0.487	5.41	37.5 ± 0.5	42.1 ± 0.5	2.184	0.076	17.3	1460	49.71 ± 0.8

Scheme 2

Micellization of (a) IPy-IL and (b)AIPy-IL in Seawater Bulk Solution and Adsorption of (c) IPy-IL and (d) AIPy-IL at the Seawater/Air Interface

Adsorption of amphiphiles based on IPy-IL and n class="Chemical">AIPy-IL at the seawater/air interface is the alternative mechanism for their surface assembly at interfaces to decrease their aggregations in the bulk seawater solution. Their surface excess concentration, Γmax, and the minimum area/molecule of ILs, Amin, are adsorption parameters that can be calculated to assess the adsorption of amphiphiles at the water/air interface. They were calculated from Gibbs equations; Γmax = (−∂γ/∂ ln c)/RT and Amin = 1016/NΓmax, where R, T, and N are the gas constant (8.314 J mol–1 K–1), the temperature (K), and the Avogadro constant (6.022 × 1023), respectively. Table shows Γmax, Amin, and (−∂ γ/∂ ln c) values of IPy-IL and AIPy-IL. The increase of the Γmax value and decrease of the Amin value of IPy-IL confirm its higher packing densities at the air/water interface (Scheme c). Moreover, the coiling of oxyethylene attached to the aromatic benzene ring of AIPy-IL decreases the hydrophobic interaction of two tetradecyl groups attached to the pyridinium ring to increase their Amin values and decreases their Γmax concentrations at the seawater/air interface (Scheme d).

One of the most important characteristics for application of amphiphiles as oilfield chemicals is based on their great ability to reduce the IFT at the crude n class="Chemical">oil/brine water interface.[40] The amphiphiles reduced the IFT of the crude oil/brine water interface below 0.1 mN/m and were used as emulsifiers for enhanced petroleum crude oil recovery.[41] In this respect, the Arabic heavy crude oil sea water IFT measurements were determined in the absence and presence different injection doses part per million (ppm; mg/L) or mM of either IPy-IL or AIPy-IL and are listed in Table . The interfacial pressure (ΔΩ; mN m–1) can be estimated from the following equation: ΔΩ (mN m–1) = Ωo – Ω d, where Ωo and Ωd are IFTs of seawater/crude oil in the presence and absence of IPy-IL and AIPy-IL, respectively. The relation between IFT measurements of petroleum crude oil/seawater and run or aging time in the presence of IPy-IL or AIPy-IL is plotted in Figure . The time (second) required to get stable IFT data was determined from Figure and is listed in Table . The data confirm that the increase of IPy-IL and AIPy-IL concentrations up to 250 mg/L greatly reduces IFTs of the crude oil/seawater interface to 14.3 and 5.8 mN/m, respectively (Table ). The increase of IPy-IL and AIPy-IL concentrations from 250 to 500 mg/L did not markedly reduce IFTs of the crude oil/seawater interface. These data confirm that the AIPy-IL reduces the IFT value more than IPy-IL in the short aging time. These data confirm the presence of imidazolium and pyridinium cations and the aromatic moiety of both IPy-IL and AIPy-IL and that they interacted with heteroatoms of asphaltenes of heavy crude oil to increase their dispersion or diffusion into heavy crude oil.[42] Moreover, the presence of the hydrophobic tetradecyl group in the chemical structure of IPy-IL and AIPy-IL facilitates their dispersion into crude oil constituents. The presence of oxyethylene in the chemical structure of AIPy-IL increases its interaction with the crude oil and seawater, which reduces IFT more than that in IPy-IL does.[43] The great ability of AIPy-IL to reduce IFT of crude oil/seawater in shorter time than IPy-IL confirms its higher interaction and absorption at the oil/water interface, which contradicts with its ability to adsorb at the seawater/air interface, as discussed before. These data prove that both IPy-IL and AIPy-IL can be used as demulsifiers at lower dose because of their great adsorption at the crude oil/seawater interface in short aging time (Table and Figure ).

Table 3

IFT and Interfacial Pressure of Sea Water/Crude Oil Interface With Different Concentrations of AIPy-IL and IPy-IL in Seawater at 25 °C

	concentration
demulsifier	(mg.L–1)	mM	IFT (mN/m)	Ω (mN m–1)	time (second)
IPy-IL	0	0	33.5	0	0
	100	0.132	25.5	8.0	600
	250	0.330	14.3	19.2	420
	500	0.660	13.2	10.3	1800
AIPy-IL	0	0	33.5	0
	100	0.098	15.3	18.2	210
	250	0.244	5.8	27.7	300
	500	0.488	2.3	31.2	1200

Figure 8

IFT measurements of crude oil droplets vs AIPy-IL and IPy-IL in seawater solution.

Application of AIPy-IL and IPy-IL as Demulsifiers

The good solubility of IPy-IL and n class="Chemical">AIPy-IL in organic solvents such as xylene, ethanol and water, besides their surface activity in reducing the water surface tension and IFT between crude oil/sea water, makes them good candidates for application as demulsifiers for different crude oil emulsions. In this respect, different compositions of Arabic crude oil/seawater (90:10, 70:30, and 50:50 volumes %) were prepared, as reported in the experimental section. The IPy-IL and AIPy-IL solutions in xylene/ethanol (75/25 volume %) with a concentration of 50 wt % were injected with different doses ranging from 100 to 500 ppm that were related to the total volume of the crude oil emulsion. The blank of each crude oil/sea water and other emulsions is prepared, but it was treated with the same dose of xylene/ethanol solvent without IPy-IL and AIPy-IL. The xylene/ethanol (75/25 volume %) was selected as the best solvent to disperse the ILs and their polymers.[12,18,19] All emulsions were heated at low temperature (45 °C) to determine their demulsification efficiencies (η %) versus aging time. All blanks were heated at 45 °C for 2 weeks without seawater separation to confirm their high emulsion stabilities. The dispersion droplet test of all emulsions indicates that all the prepared emulsions were dispersed in toluene to confirm that crude oil and seawater form continuous and dispersed phases, respectively. Consequently, all emulsion types are W/O emulsions, which are responsible for their higher stability. The demulsification data such as η % and demulsification time (h) of all emulsions were determined and are listed in Table . The photographs of demulsification of 90:10 and 70:30 volume % emulsions in the absence and presence of IPy-IL and AIPy-IL were selected and are shown in Figure a–d. The relation of η % versus demulsification time (h) of all the prepared emulsions is shown in Figure a–c.

Table 4

Demulsification Efficiency of the Prepared AIPy-IL and IPy-IL for Crude oil/Seawater Emulsion at Different Times at Temperature 45 °C

		crude oil/seawater emulsions (vol. %)
		90:10		70:30		50:50
compound	dosage (ppm)	η %	time (h)	η %	time (h)	η %	time (h)
IPy-IL	100	100	6	80	10	32	10
	250	100	4	73	7	40	12
	500	100	5	73	8	28	10
AIPy-IL	100	100	4	100	6	32	10
	250	100	2	86.5	6	32	10
	500	100	4	86.5	8	36	10

Figure 9

Demulsification photographs of (a) 90:10 in the presence IPy-IL, (b) 90:10 in the presence of AIPy-IL, (c) 70:30 in the presence IPy-IL, and (d) 70:30 in the presence of AIPy-IL volume % crude oil: seawater emulsion at different times at temperature 45 °C.

Figure 10

Demulsification efficiency of the prepared AIPy-IL and IPy-IL for (a) 90:10, (b) 70:30, and (c) 50:50 volume % crude oil: seawater emulsion at different times at temperature 45 °C.

Careful inspection of the demulsification data of different crude oil/sean class="Chemical">water emulsions (Table and Figures and 10) confirms the formation of stable emulsions due to higher salinity of seawater (36,170 mg/L) and asphaltene content of crude oil (8.3 wt %; Table ). The particle sizes of the prepared emulsions (determined by DLS; not represented here for brevity) were found to be 2.5, 4, and 6 μm for 90:10, 70:30, and 50:50 (crude oil/seawater volume %) emulsions, respectively. This means that the particle sizes of emulsions are low and increase with the increasing seawater content. Moreover, using the lower particle sizes of crude oil/sea water emulsions, the order of emulsion stability can be arranged in the order 90:10 > 70:30 > 50:50 volume %. The demulsification data (Table and Figures and 10) show that both IPy-IL and AIPy-IL demulsify the 90:10 emulsion with higher efficiency (100%) at lower dose 100 ppm as well as higher injection dose (500 ppm). It is also noticed form the demulsification data (Figures and 10a; Table ) that AIPy-IL demulsifies the 90:10 emulsion in shorter demulsification time more than IPy-IL using different injection doses. These data can be correlated with IFT data (Table and Figure ), which confirm the greater efficacy of AIPy-IL to adsorb at the crude oil/seawater interface in shorter time more than IPy-IL. It is also observed that only AIPy-IL demulsifies 70:30 emulsion (η % is 100%) using the 100 ppm injection dose (Figure c–d and 10b). AIPy-IL and IPy-IL fail to demulsify 50:50 emulsion with higher demulsification efficiencies (Table , Figure c), but IPy-IL demulsifies this crude oil emulsion with greater efficiency than IPy-IL. This can be attributed to the greater solubility of IPy-IL in seawater than AIPy-IL, as confirmed from its greater RSN value. By comparing the η % of the AIPy-IL and IPy-IL with the previous data for application of ILs and germinal ILs as crude oil demulsifiers,[17−19,22,44−46] it was found that the present prepared ILs have greater efficiency to demulsify petroleum crude oil emulsion at lower concentrations of 100 ppm, lower demulsification time, and low temperature 45 °C. It is reported that previous ILs demulsify the same crude oil emulsion at higher demulsifiers doses, demulsification time, and temperature of 500–2000 ppm, 6–12 h, and 65 °C, respectively.[17−19,22,44−46]

The optical microscopy photographs of crude oil sean class="Chemical">water emulsions 70:30 and 50:50 volume % in the presence of 100 ppm of AIPy-IL are represented in Figure a–d to prove the demulsification mechanism of the prepared ILs. It is noticed that the particle sizes of the water droplet increases with small water droplet at big water droplets surrounded by AIPy-IL for 70:30 emulsion (Figure a,b). The AIPy-IL slightly increases the seawater droplet and cannot remove the asphaltene layers surrounded by the W/O droplet of 50:50 volume % emulsion (Figure c,d). Moreover, the AIPy-IL orients the seawater droplets to join the AIPy-IL network (as shown in Figure d) that cannot easily demulsify the 50:50 volume % emulsion with higher efficiency as well as occurred with 90:10 and 70:30 volume % crude oil seawater emulsions. These data prove that the greater tendency of the prepared AIPy-IL and IPy-IL to adsorb at the seawater/crude oil interface increases their diffusion through W/O emulsion type in short time. Their high amphiphilicity tends to orient either their polar heads (the cationic and anionic parts of the pyridinium and imidazolium) toward the seawater phase or the hydrophobic tail (tetradecyl and aromatic) toward the oil phase. The oxyethylene of AIPy-IL and aromatic phenols of IPy-IL interact with the rigid asphaltene layers surrounded by the water droplet to disperse into a continuous crude oil phase to facilitate the coalescence of the seawater droplets and their salts from the oil phase. The increase of AIPy-IL concentrations more than 250 up to 500 ppm that reduces their demulsification can be due to the aggregation of AIPy-IL and accumulation of asphaltenes in the water–oil interface.[47] Water content (WC) was measured in the crude oil phase for the emulsion containing 30% water, treated with AIPy-IL and IPy-IL at different concentrations after demulsification using the Karl–Fischer instrument (Figure ). It was observed that the optimum concentration of both AIPy-IL and IPy-IL agrees with the data reported in Table , which confirm the abovementioned discussions, including the effect of demulsifier concentration, chain length, and time.

Figure 11

Optical microscope photographs of (a) 70:30 blank, (b) 70:30 using 100 ppm of AIPy-IL, (c) 50:50 blank, (b) 50:50 using 100 ppm of AIPy-IL crude oil: seawater emulsions.

Figure 12

WC in the crude oil phase for the emulsion containing 30% water treated with AIPy-IL and IPy-IL at different concentrations after demulsification times.

The separation of the prepared AIPy-IL and IPy-IL after recovery from the water phase by using a rotary evaporator shows the same FTIR characteristics (Figure a,b). The data confirm that there are no crude oil droplets separated or dispersed in the water phase and also elucidate that the AIPy-IL and IPy-IL cannot be destroyed during the demulsification process. Reusing the AIPy-IL and IPy-IL into five cycles for 90:10 volume % emulsion at 100 ppm confirms the same results obtained in the first runs for five cycles. These data confirm that AIPy-IL and IPy-IL were not thermally or chemically aged in harsh salt conditions for several cycles.

Conclusions

New amphiphilic tricationic n class="Chemical">imidazolium–pyridinium bromide acetate salts have been prepared, and their thermal characteristics confirm that they have Tm values below 100 at 87–89 and 70–71 °C, and they are ILs. The presence of an aromatic phenol in the chemical structure of IPy-IL increases its rigidity and Tg value at −16.8 °C (Figure a) to be more than the Tg value of AIPy-IL determined at −53.9 °C. The incorporation of a polyethoxy group in the chemical structure of AIPy-IL increases its flexibility after ethoxylation of the OH phenol group of IPy-IL because of the breaking of the hydrogen bond of phenol groups, which increases IPy-IL rigidity and Tm and Tg values. Moreover, the presence of polyoxyethylene increases the thermal stability of AIPy-IL more than IPy-IL and lowers the protonation of acetate anions because of disappearance of the phenol to phenoxy group. Both IPy-IL and AIPy-IL are soluble in seawater and behave as amphiphiles to adsorb at interfaces and form micelles in the bulk seawater solution. Both IPy-IL and AIPy-IL form polydisperse aggregates at their cmc values, as elucidated from increasing their PDI value greater than 0.7 (Figure a,b).The low surface charges of IPy-IL at 7.05 mV and high surface charge of AIPy-IL at 49.7 mV indicated that IPy-IL and AIPy-IL molecules form a neutral bilayer and multilayer micelles. The coiling of oxyethylene attached to the aromatic benzene ring of AIPy-IL decreases the hydrophobic interaction of two tetradecyl groups attached to the pyridinium ring to increase their Amin values and decreases their Γmax concentrations at the seawater/air interface. The IPy-IL and AIPy-IL reduced the IFT of the crude oil/seawater interface in a shorter time than IPy-IL at concentrations up to 250 mg/L greatly; their values are 14.3 and 5.8 mN/m. Both IPy-IL and AIPy-IL demulsify the 90:10 emulsion with higher efficiency (100%) at a lower dose of 100 ppm. Only AIPy-IL demulsifies 70:30 emulsion (η % is 100%) using a 100 ppm injection dose, and it was reused for five cycles to demulsify 90:10 volume % emulsion at 100 ppm.