Synthesis and Application of Poly(ionic liquid) Based on Cardanol as

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Synthesis and Application of Poly(ionic liquid) Based on Cardanol as Demulsifier for Heavy Crude Oil Water Emulsions Abdelrhman O. Ezzat, Ayman M. Atta, Hamad A Allohedan, Mahmood M.S. Abdullah, and Ahmed I. Hashem Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b02955 • Publication Date (Web): 30 Nov 2017 Downloaded from http://pubs.acs.org on December 1, 2017

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Synthesis and Application of Poly (ionic liquid) Based on Cardanol as Demulsifier for Heavy Crude Oil Water Emulsions by Abdelrhman O. Ezzat1, Ayman M. Atta1,2,* Hamad A. Al-Lohedan1, Mahmood M. S. Abdullah 1 and Ahmed I. Hashem3 1

Surfactants research chair, Chemistry department, college of science, King Saud University, Riyadh 11451, Saudi Arabia. (* E-mail: [email protected])

2

Petroleum Application Department, Egyptian Petroleum Research Institute, Nasr City 11727, Cairo, Egypt. 3

Chemistry department, faculty of Science, Ain Shams University, Abasia, 11566 Cairo, Egypt. Abstract: Amphiphilic poly (ionic liquids), PILs, derived from natural products attracted great attention as a green chemical in the field of the surface chemistry and petroleum industry. In the present work, new surface active PILs were synthesized from cardanol cashew nut oil as a hydrophobic alkyl phenol. The phenol group was etherified with diethanolamine, ethanolamine and tetraethylene glycol using linking agent based on β,βdicholorodiethylether to insert nonionic hydrophilic groups into cardanol. The

amine

group

was

quaternized

with

2-acrylamido-2-methyl-1-

propanesulfonic acid to produce polymerizable ionic liquids that polymerized to obtain new PILs. The chemical structure of the prepared new PILs was elucidated from 1HNMR and elemental analysis. The surface activity of the prepared PILs was determined from the surface and interfacial tension measurements of their aqueous solution. The ability of the prepared PILs to disperse the asphaltene fractions of the heavy Arabian crude oil was studied. It was used to explain their demulsification performance and

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efficiency data when they used as demulsifiers for crude oil water emulsions. The demulsification data elucidate that, the PILs have greater ability to reduce IFT can separate water effectively. Moreover, the PILs have greater tendency to disperse asphaltene perform better as demulsifier than that flocculate asphaltenes. Keywords: Poly(ionic liquid), Arabic heavy crude, emulsions, demulsifier, asphaltene dispersants. 1. Introduction: Crude oil water micro- multiple, and stable emulsions such as water-in-oil (W/O) or water-in-oil-in-water-in-oil (W/O/W/O) are highly undesirable in the petroleum industry because they caused corrosion for the steel, pump failure and undesirable in the refining operations [1-3]. These emulsions are very stable due to the formation of stable films at water or oil droplets which produced either from crude oil components such as asphaltene, resins or from oilfield chemicals that used for the different crude oil production operations [4-6]. There are different demulsification techniques used to separate water from crude oil emulsions such as mechanical, thermal, electrical and chemicals demulsification methods [7-9]. The chemicals demulsification method attracted great attention among these different demulsification techniques due to their rapid and higher demulsification efficiency of the crude oil emulsions than other techniques [7-9]. The chemicals used for the demulsification of crude oil water emulsions were formulated from the different types of nonionic surfactants blends. Their chemical structures were based on both hydrophilic part such as polyoxyethylene and hydrophobic parts based on polyoxypropylene [10], alkyl phenol formaldehyde ether [11], alkyl fatty ester and amide [12]. These

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surfactants should have a great tendency to adsorb at oil or water droplet to replace the stable asphaltene films and they are capable of occupying the oil/water interface [13-15]. However, these chemicals are toxic, expensive and un-ecofriendly. Therefore, the design of new active, cheap and ecofriendly bio-chemicals as demulsifiers is still in demands. In this respect, the preparation and applications of the new ionic liquids (ILs) from bio-based materials were reported as alternative demulsifier oilfield chemicals [16, 17]. Recently, the green chemicals based on ILs were used to solve the crude oil water emulsion problems with high water removal efficiency for W/O emulsion in a short demulsification time [18, 19]. In this work, cardanol as bio-materials is selected to prepare new amphiphilic IL to apply as environmentally friendly demulsifier for the stable heavy crude oil water emulsion. Cardanol was extracted from cashew nut shell and its composition contained m-pentadecyl phenol [20]. Its chemical structure attracted more attention to prepare amphiphiles to replace the alkyl phenols produced from the petrochemicals which used as oilfield chemicals [21-24]. Moreover, the chemical structure of cardanol molecule was modified to prepare new smart amphiphilic ILs [25, 26]. In our previous works [18, 19], the mechanism for demulsification of the crude oil water emulsion in the presence of ILs or poly (ionic liquids) (PILs) was illustrated. It was reported that, the IL or PILs having a greater tendency to diffuse in the continuous phase of the crude oil water emulsions with formation of networks achieved high demulsification rate. Accordingly, the present work aims to synthesize new class of PILs surfactants from cardanol to apply as demulsifiers for the Arabic heavy crude oil water emulsions. The etherification of cardanol phenolic groups with ethanol amines followed by quaternization with poly 3


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(2-acylamido-2-methyl propane) sulfonic acid polymer is proposed to prepare PILs. It is expected that the prepared PILs have unique surface active characteristics will perform better at water/oil emulsion interface. The applications of the prepared cardanol PILs to act as asphaltenes dispersants and demulsifier for the heavy crude oil emulsions are another goal of the present study.

2. Experimental 2.1. Materials All chemicals used to synthesize PILs were obtained from Sigma-Aldrish chemicals Co. and they used without further purification. Cardanol extracted from Cashew nut shell oil was purchased by Shanghai Judong Trading Company

Ltd.),

ethanolamine,

diethanolamine

(DEA),

β,β-

dicholorodiethylether (DCDE), epichlorohydrine (ECH), tetraethylene glycol (TEG) and sodium hydroxide, were used to modify the chemical structure of cardanol with hydrophilic group. 2-Acrylamido-2-methyl-1propanesulfonic acid (AMPS), 2,2-azobisisobutyronitrile (AIBN) were used to quaternize modified cardanol amphiphiles to obtain polymerizable ionic liquid. Heavy Arabic crude oil (20.8 API), its water and asphaltene contents were 0.145 and 6 wt.% respectively, produced from Ras Tanoura wells by Aramco, Saudi Arabia was used with sea water of Arabic Gulf to formulate the synthetic emulsions as reported in the previous work [19]. The asphaltene fractions were precipitated from the crude oil using ASTM D2007. The mixed solvent of toluene: n-heptane (1:40 Vol. %) was used to precipitate asphaltenes from the crude oil.

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2.2. Preparation methods a) Preparation of QDECA Cardanol (0.04 mol; 11.93 g), DEA( 0.04 mol; 4.2 g), DCDE (0.04 mol; 5.7 g) were mixed with NaOH powder (0.08 mol; 3.2 g) under stirring and in the presence of N2 atmosphere. The reaction mixture temperature was increased up to 150 oC and kept constant for 4h. Acetone solvent (50 mL) was added at the end of reaction to precipitate NaCl from the cooled reaction mixture. The NaCl was separated from the reaction mixture by filtration. Acetone solvent was removed from the filtrate by using rotary evaporator under reduced pressure. DCDE (0.08 mol; 11.44 g), TEG (0.08 mol; 15.53 g) and NaOH powder (0.16 mol; 6.4 g) were added to the reaction mixture. The reaction mixture temperature was increased up to 100 oC for 5h under stirring in the presence of N2 atmosphere. Acetone solvent (100 mL) was added to precipitate NaCl. The NaCl and acetone were separated from the reaction mixture by filtration and vacuum distillation, respectively.

The

unreacted TEG, NaOH and DCDE were removed by dilution the reaction mixture with isopropanol followed by washing with hot saturated aqueous solution of NaCl in separated funnel. The pure di-etherified cardanoxy amine (DECA) surfactant was separated from the isopropanol organic using rotary evaporator. DECA (0.005 mol; 5.01 g) was mixed with equimolar of AMPS (0.005 mol; 1.036 g) in the presence of DMF (25 mL) and AIBN (0.1 Wt. % from the weight of AMPS) as a solvent and initiator, respectively. The reaction mixture was stirred and heated at 70 oC under N2 atmosphere for 24h. The DMF was removed at the end of the reaction using rotary evaporator to

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obtain viscous liquid of quaternized di-etherified cardanoxy amine (QDECA). The preparation scheme of QDECA was represented in the Scheme 1.

Scheme 1: Synthesis route of QDECA as new PIL.

b) Preparation of QTECA Cardanol (0.1 mol; 29.8 g) was mixed with excess of ECH (0.3 mol; 27.7 g) and NaOH (0.1 mol; 4g dissolved in 5 mL of water) under stirring. The reaction mixture was refluxed under N2 atmosphere for 9 h. The NaCl precipitate was removed from the cooled reaction mixture by filtration. The excess of ECH was separated from the filtrate using rotary evaporator. The unreacted NaOH was also removed by washing the remained reaction mixture with water until the pH of water equals 7. The purified dark brown liquid was stirred with ethanol amine (0.1 mol; 6.1 g) and heated at 100 oC under N2 atmosphere for 5h. TEG (0.09 mol; 17.5 g), DCDE (0.09 mol; 12.8 g), toluene (50 mL) and NaOH pellets (0.09 mol) were added to the cooled

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reaction mixture. The reaction temperature was increased and kept constant at 120 oC for 6h under N2 atmosphere. The NaCl white precipitate was separated from the cooled reaction mixture by filtration. Toluene solvent was removed from the reaction filterate by using rotary evaporator. The unreacted TEG, NaOH and DCDE were removed as reported in above section to obtain pure tri-etherified cardanoxy amine (TECA). The pure TECA (0.003 mol; 3.95 g) was quaternized and polymerized with equimolar of AMPS (0.003 mol; 0.621 g) in the presence of DMF ( 25 mL) and AIBN (0.1 Wt. % from the weight of AMPS) as solvent and initiator, respectively. The polymerization and quaternization temperature was maintained at 70 oC for 24h under N2 atmosphere to obtain QTECA. preparation scheme of QTECA was represented in the Scheme 2.

Scheme 2: Synthesis route of QTECA as new PIL.

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The

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2.3. Characterization of PILs The chemical composition included N and S contents of the prepared PILs were estimated from the elemental microanalysis.

The N analysis was

performed on a Carlo Erba 1106 elemental analyzer, and the S content was estimated by the Leco SC 32 sulfur analyzer (ASTM 4239-93). The expected chemical structure of the prepared PILs was investigated by proton magnetic nuclear resonance, 1HNMR and

13

CNMR spectroscopy

model a 400MHz Bruker Avance DRX-400 spectrometer. The interfacial and surface tension measurements of the different concentrations of QDECA and QTECA in water were recorded by pendant drop method using drop shape analyzer (DSA-100). The solubility of the prepared PILs in water was estimated from their relative solubility number (RSN). The PIL (2g) solubilized in 60 mL of the solvent solution (consisting of 97.4 wt.% ethylene glycol diethylether and 2.6 wt.% toluene) was titrated against water [27]. The volume of water (mL) used to obtain turbid PILs solutions represent their RSN values. The determined volume of water (mL) was recorded as RSN value. The aggregations of QDECA and QTECA in water, and asphaltenes in the absence and presence of QDECA and QTECA into the toluene / heptane solvent were measured by dynamic light scattering (DLS). It was used to determine

the

hydrodynamic

diameter

of

aggregates

(Dh;

nm),

polydispersity index (PDI) and their zeta potentials in water using (Zetasizer Nano ZS, Malvern Instrument Ltd., Malvern, UK) at 25 oC. Zeta potentials (mV) of QDECA and QTECA were determined from their aqueous solutions that contain 0.001 M KCl at 25 °C. The size and shape of the crude oil/

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seawater emulsions were confirmed by using Optical microscope (Olympus BX-51 microscope attached with a 100 W mercury lamp). 2.4. Asphaltene dispersing efficiency of ILs The dispersion efficiency (Eff %) of the prepared PILs as asphaltene dispersant was calculated as reported in the previous work [28]. Mixture of toluene (used as asphaltene solvent) and n-heptane (as asphaltene precipitant) were used to investigate the dispersion ability of the prepared PILs as asphaltene dispersant. Toluene: n-heptane solvents ( 1:40.4 Vol. %) used to isolate the asphaltene fractions from crude oil according to procedure ASTM D2007 was selected to determine the asphaltene dispersion efficiencies. The asphaltene that remains in toluene after precipitation with n-heptane was evaluated via UV-vis spectroscopy at ambient temperature. In this respect, the asphaltene toluene solution (1 mL; 5.0 g L−1) toluene was blended with n-heptane (40.4 mL) under vigorous stirring at ambient temperature and recorded as reference sample. The same quantity of asphaltene solution was blended with different weight contents of the prepared QDECA and QTECA (ratio of PIL: asphaltene was ranged from 1:1 to 1:5 Wt %) with continuous stirring for 5h. The same amount of nheptane (40.4 mL) was added to the asphaltene and PIL toluene solution. The absorbance of the suspended asphaltene in n-heptane/toluene solution was determined for reference (Ar) in the absence of PILs using UV-vis spectrometer at the wavelength of 390 nm. The absorbance of suspended asphaltene in n-heptane/toluene solution in the presence of PIL solutions (As) was also determined from UV-vis spectrometer at the same selected wavelength. The % Eff of ILs as an asphaltene dispersant was determined from the relationship: %Eff = [(As×100)/Ar].

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The particle sizes for the asphaltene separated after centrifuge their solutions in toluene/n-heptane at 2000 rpm for 25 min were determined from DLS measurement.

2.5. Demulsification of the crude oil water emulsions Different compositions of the crude oil sea water emulsions ranged from 50/50 to 90/10 Vol % were formulated with vigorous stirring using homogenizer at speed 10000 rpm. The prepared PIL was dissolved with solvent mixture of xylene / ethanol (75/25 Vol. %) to obtain PIL concentrations of 30 Wt %. The PIL solution was injected in the crude oil water emulsion at different concentrations ranged from 10 to 100 mgL-1. The reference or blank sample is used to compare the demulsification results of the crude oil emulsions in the absence of PILs and presence of solvent (xylene/ethanol; 75/25) without PILs. The solvent was injected into the crude oil water emulsions at the same concentration doses. The demulsification efficiencies (η %) and demulsifier performances ( µ ; mL min-1) were determined for different crude oil/ water emulsion at 60 oC as reported in the previous wok [19]. The η % was determined as η %= Vs/Ve; where Vs and Ve are the separated volume of water at definite time and total emulsified water, respectively. The µ was also calculated as µ = V/t; where V and t are the separated volume of water at definite time and time of separation (minute), respectively. The separated water from demulsification experiment was acidified with sulfuric acid to pH (2 to 3), and the oil was extracted twice by 2 mL of isooctane to determine the residual oil in water. The concentration of oil in

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isooctane was measured by using the UV-VIS (PerkinElmer, model Lambda 35) at λmax of 255 nm. The residual water in the separated crude oil was analyzed by the Coulometric Karl Fischer titration ASTM-D4928-12 using a Metrohm Karl Fischer Titrator model 870 KF Titrino Plus. All measurements used in this work were carried out in triplicate to determine their average values.

3. Results and discussion The present work aims to modify the chemical structure of cardanol to obtain new PIL based on QDECA and QTECA as represented in the schemes 1 and 2, respectively. The aim of the work was extended to modify the hydrophobic chemical structure of the cardanol by incorporation of the hydrophilic amines such as EA and DEA followed by ethoxylation their hydroxyl groups with TEG in the presence of linking agent DCDE as represented in the experimental section. The QDECA was prepared by etherification of cardanol with DEA in the presence of linking agent DCDE and sodium hydroxide as a catalyst (Scheme 1). The QDECA reaction yield percentage is 99.3 %. The N and S contents were determined as 2.38 and 2.60 %, respectively. The calculated N and S contents (wt. %) of QDECA, based on the molecular weight of one repeating unit as 1210 g.mol-1, are 2.31 and 2.64 (wt. %), respectively. The QTECA was prepared by etherification of cardanol with ECH, ethanolamine and TEG in the presence of DCDE and NaOH as linking agent and catalyst, respectively (Scheme 2). The reaction yield percentage of viscous liquid QTECA is 97.8 %. The N and S contents were determined as 1.89 and 2.11 %, respectively. The calculated N and S contents of QTECA, based on the molecular weight of 11


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one repeating unit as 1525 g.mol-1, are 2.31 and 2.64 (wt. %), respectively. The determined N and S contents of QDECA and QTECA agree with their calculated content and elucidate the purity of the prepared PILs. The produced DCEA and TECA are quaternized with AMPS monomer in the presence of AIBN as radical initiator to obtain ammonium salt QDECA and QTECA derivatives as new PILs. The chemical structures of QDECA and QTECA are elucidated from 1

HNMR and 13C NMR as represented in Figures 1 and 2, respectively. The

1

HNMR spectra of QDECA and QTECA (Figure 1 a and b) confirm the

presence of cardanol hydrophobic moieties with the presence of both the four aromatic protons between 6.73 and 7.21 ppm and the non-conjugated olefinic protons between 4.89 and 6.12 ppm in all spectra. The saturated protons of cardanol, methylene and methyl, are observed between 0.83 and 2.95 ppm as multiples, in all spectra (Figure 1a –b) [20]. The formation of the oxyethylene units in both QDECA and QTECA is confirmed from the appearance of a new multiple peaks in the region between 3.41 and 4.13 ppm accounting for their newly introduced ethoxy amines and hydroxy group protons (Figure 1 a and b). It is also observed that, the integration curve for area under the signal groups of QTECA is higher than that obtained for QDECA to confirm the formation of the triethoxy groups of QTECA as represented in both schemes 1 and 2. Moreover, the comparison the integration of the protons of the hydroxyl group, at 3.05 ppm, with the integration curve for four aromatic protons, 6.73 and 7.21, for both QDECA and QTECA elucidates that there are more hydroxyl groups introduced in QTECA more than QDECA. The presence of AMPS polymer in both chemical structure of QDECA and QTECA is confirmed from N and S contents and elucidated from NMR spectra (Figures 1 and 2). The 12


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appearance of the peaks having the chemical shifts at 1.44, 1.97, 3.2 and 4.6 ppm attributed to the hydrogens of CH3 groups, the methylene of the main backbone chain, CH2 group bonded to SO3, and the hydrogens of the CONH, respectively confirms the presence of AMPS polymer (Figure 1 a and b) [29]. The appearance of new peak at 8.45 ppm, Figure 1 a and b, confirms the quaternization of amine groups with sulfonate group of AMPS in both [29].

Figure 1: 1HNMR spectra of a) QDECA and b) QTECA.

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The 13C NMR spectra of both QDECA and QTECA (Figure 2 a and b) are also used to confirm their chemical structures. The peaks at 176.51, and 52.16 ppm attributed to CONH of AMPS and C-NH+ of quaternized QDECA and QTECA elucidated the formation of PIL amine salts of AMPS with ethoxylated amine derivatives of cardanol [30]. More details of the other peaks are assigned in the chemical structures of QDECA and QTECA as represented in Figures 2 a and b, respectively. The 1HNMR and

13

C

NMR confirm the presence of both ethoxylated amine derivatives of cardanol and PAMPS in their chemical structure with the formation of new PILs.

Figure 2: 13CNMR spectra of a) QDECA and b) QTECA.

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3.2. Solubility and surface activity of PIL It is very important to evaluate the surface activity and the surface properties of ILs and PILs due to their application in different processes occurring at the surface or interface of the ILs [31-34]. The surface activity of ILS and PILs are controlled by the selection of the suitable chemical structure cations and anions tailored for the desired industrial applications [31-34]. In this respect, the surface activity of the prepared QDECA and QTECA was determined from the surface tension measurements to investigate the effect of their chemical structures on their surface properties. The surface tension measurements also used to understand the inter- and intra-molecular interactions of PILs in the bulk solution and at air/water interface. Accordingly, the surface tension measurements are essential not only for the surface science but also for the practical applications of ILs or PILs. It is also very important to investigate the solubility of QDECA and QTECA by measuring the RSN as reported in the experimental section and listed in Table 1. The RSN provides a practical alternative to the hydrophilic– lipophilic balance (HLB) used for assessing the nonionic surfactants [27]. It was reported that the nonionic surfactants having HLB below 8 possess RSN value < 13 which are considered insoluble in water. While nonionic surfactants having HLB between 8 to 11 with1317 are dispersible at low concentrations. Moreover, the nonionic surfactants have HLB more than 11 their solubility in water is confirmed by a RSN value > 17. The RSN values of QDECA and QTECA are 16.4 ± 0.3 and 15.2 ± 0.2 mL, respectively which confirm that the prepared PILs are soluble in water at low concentration. Moreover, the QDECA is soluble in water more than QTECA. This means that the QDECA is more polar and its polar groups require more water to become turbid than QTECA which has high TEG 15


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contents. This means that, the increase of branching of QTECA decreases their solubility in water and prevents the dehydration of hydrophilic groups with water. The relation between the surface tension measurements of PILs, QDECA and QTECA, and their different concentrations in aqueous solution at 25 oC (ln c; mol.L-1) are represented in Figure 3. The concentrations of QDECA and QTECA (mol.L-1) are calculated from their theoretical molecular weight of the individual repeating units determined as 1210 and 1525 g.mol-1, respectively. The plateau curves of QDECA and QTECA, (Figure 3) show only one adsorption isotherm and they did not show any valley to confirm that the prepared QDECA and QTECA are pure and they did not contain any impurities [31]. Moreover, the adsorption isotherm of QDECA and QTECA (Figure 3) confirm the reduction of the water surface tension by a very small amount of monolayer of QDECA and QTECA. The critical aggregation concentration, cac; mol. L-1) and the surface tensions at cac ( γcac; mN.m-1) are measured from Figure 3 and listed in Table 1. The low cac of QTECA confirms its lower solubility in water as determined from RSN value. Also, the QTECA reduces the surface tension of water at low concentration more than QDECA. It is also observed that the QDECA has greater tendency to reduce the surface tension of water at γcac more than QTECA. This means that the adsorption of QDECA increased more than QTECA and influenced by cardanol cations. Their PAMPS anions do not control the adsorption process and do not significantly affect the surface tension.

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Figure 3: Relation between the surface tension and different concentrations for aqueous solutions of QDECA and QTECA at 25 oC. Table 1. Solubility and surface activity data of QDECA and QTECA in water at 25 oC.

compounds

QDECA QTECA

RSN (mL of water)

Zeta potential (mV)

16.4 ± 0.3 15.2 ± 0.2

-8.1± 1.1 67.0± 4.3

cac γcac mmol/L mN/m 0.49 0.11

35.6 43.2

Гmax × 10

∆γ mN/m

(−∂γ/∂lnc)T

36.6± 0.1 28.9± 0.1

10.8 8.2

10

µmol/ m2 4.50 0.037 3.44 0.048

The aggregation of QDECA and QTECA in water and at air/ water interface are also investigated from the particle size and zeta potential measurements as represented in Figures 4 and 5, respectively. The hydrodynamic diameter of aggregates (Dh; nm) and PDI values of QTECA (Figure 4 a) have uniform and lower sizes than QDECA (Figure 4 b). This means that the QDECA forms different sizes of aggregates at cac which required high concentration of QDECA. The zeta potentials or surface charges of QDECA and QTECA aggregates (figure 5 a and b) confirm that the QDECA

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Amin nm2

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aggregates possess negative charges to elucidate the hydrophobic part of cardanol cations assembled in the interior of micelle and its sulfonate anions of PAMPS arranged at the exterior surface of aggregated micelles. The positive surface charge of QTECA (Figure 5 b) elucidates that the PAMPS backbone assembled to the interior of aggregates and the cardanol cations adsorbed at the surface of the aggregates. These data proved that both QDECA and QTECA behave different aggregates performances in the bulk water solution and their cations and anions aggregate to form the micellelike structures. Therefore, it is concluded that the QDECA anions adsorb at the micelle surface to interact with cardanol cations as well as aggregating. This arrangement may cause the change in the orientation the hydrophobic parts of cations. Such segregation of the cation and anion distribution also occurs at the interfacial region of other IL aqueous solutions [33]. The high reduction of the surface tension of water for QDECA more than QTECA confirms the weak intermolecular interaction between ions (low zeta potential values) as well as the hydrophobicity of cardanol cations [34].

Figure 4: DLS data of a) QTECA and b) QDECA in aqueous solution concentrations of 150 and 600 mg.L-1, respectively at 25 oC. 18


Page 18 of 38

Page 19 of 38 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 5: Zeta potential data of a) QDECA and b) QTECA in aqueous solution concentrations of 600 and 150 mg.L-1, respectively and 0.001 M of KCl at 25 oC. The adsorption of QDECA and QTECA at air/water interface is investigated from the surface excess concentration, Г

max,

and the minimum area of

molecules, Amin, at the aqueous–air interface. The Г the following relation: Г

max

max

is calculated from

= (-∂ γ / ∂ ln c)T /RT, where (−∂γ / ∂ ln c)

T

is

the slope of the plot of γ versus ln c at constant temperature (T) and R is the gas constant (J mol−1 K−1) [35]. The Amin is investigated from the equation: Amin = 1016/ N Гmax, where N is Avogadro’s number. The data of Гmax, Amin, and (-∂ γ / ∂ ln c) are determined and listed in Table 1. The data of Гmax and Amin confirm the presence of branching in the chemical structure of QTECA increases their interaction with water at air/water interface to decreases their

19


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

concentrations and increases their surface area at interfaces. Moreover, the good dipole-dipole interaction between sulfonate anion and amine cations of QDECA increases the tighter packing of QDECA at interfaces to increase its concentration by increasing the Г

max

and lowering the Amin to denser

arrangement of their cardanol hydrophobic groups [36]. These results conclude that, the QDECA and QTECA behave as surfactants due to its successive adsorption of both cations and anion at interfaces [37].

3.3. Interaction of QDECA and QTECA with asphaltene Asphaltene is one of the heavy fractions of the crude oil, even at low concentrations, has a tendency to stabilize the water droplet in the crude oil to form emulsions, aggregate and precipitate, generating serious problems during the crude oil production, transportation and refining [38-40]. There are many surfactants based on alkyl phenols were used to demulsify the crude oil emulsions with destabilization of asphaltenes [41]. Moreover, the cardanol polymers were used as asphaltenes dispersant [27]. Moreover, it was found that the ability of additives to disperse the asphaltene in the crude oil increases the demulsification results [27]. In this respect, the ability of the QDECA and QTECA as PILs to disperse the asphaltene is investigated from %Eff values and asphaltene aggregation diameters as determined from the experimental section and listed in Table 2 and Figure 6 a-c, respectively.

20


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Energy & Fuels

Table 2: Dispersion efficiencies of QDECA and QTECA toluene solution for asphaltene in n-heptane at 25 oC. Ratio of PIL:Asphaltene

%Eff. of PILs as asphaltene dispersants QDECA

DLS

DLS

QDECA

QTECA

Dh

QTEC A

(nm)

PDI

Dh

PDI

(nm)

Asphaltene

-

-

2826

0.981

2826

0.981

1:5

18.74

48.04

2784

0.781

1650

0.452

1:4

33.32

55.67

2345

0.653

1213

0.382

1:3

42.56

65.42

1914

0.541

980

0.313

1:2

50.34

70.35

1580

0.482

540

0.256

1:1

56.46

75.09

1316

0.407

261

0.125

The data of asphaltene dispersion efficiencies ( % Eff) and reduction size of asphaltene aggregates (Table 2) confirm the higher ability of QTECA to adsorb at the surface of asphaltene aggregates more than QDECA. The asphaltene aggregates formed due to the increase of the asphalteneasphaltene interactions more than toluene / asphaltene interactions [42]. The reduction of the hydrodynamic diameters (Dh; nm) of the asphaltene aggregates with the presence of QDECA or QTECA was correlated to the charge-transfer interactions and the spatial arrangement of the PILs [28]. In the previous section, it was found that the hydrophobicity of QTECA increased in water more than QDECA due to strong hydrophobic interactions of QTECA cations, which facilitate the adsorption of QTECA cations at the interfaces. The increasing of asphaltene dispersion efficiencies

21


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of QTECA more than QDECA can be referred to adsorption of positive charges cardanol cations on the asphaltene negative charges. This interaction was reduced the repulsion between the negative charges of QDECA anions with asphaltene as confirmed from zeta potential measurements. It was also expected that the QTECA cardanol hydrophobic cations would achieve higher asphaltene dispersion due to the higher interaction of its alkyl phenol with n-heptane [43, 44].

Figure 6: particle sizes of asphaltenes a) absence of PILs, b) QTECA and c) QDECA (asphaltene : PIL; 1:1 )in toluene/heptane solvent. The IFT data of the heavy Arabic crude oil with different concentrations of QTECA and QDECA in the seawater are measured and represented in

22


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Page 23 of 38 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 7. The interfacial pressure (Ω; mN m-1) was calculated from the relation: Ω (mN m-1) = γo - γd where the γd or γo is referred to the interfacial tension with or without PILs, respectively. The data of Ω are calculated and listed in Table 3. The data confirm that the QDECA has high Ω value than QTECA that confirm the greater tendency to reduce the IFT more than QTECA. Moreover, the IFT data are reduced with increasing the QTECA and QDECA concentrations. The previous data confirm that the QTECA has greater tendency to disperse the asphaltene in the crude oil more than QDECA. The surface activity data also confirm that the good dipole-dipole interaction between sulfonate anion and amine cations of QDECA which increases the tighter packing of QDECA at interfaces. The chemical structure of QDECA (scheme 1) is less sterically hindered than QTECA (scheme 2) which increases its tendency to irreversibly adsorb at the wateroil interface [45, 46]. Hence, the interfacial activity of QDECA will increase more than QTECA when they dispersed in the water.

Figure 7: IFT data of heavy Arabic crude oil with different concentrations of QDECA and QTECA at 25 oC.

23


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Table 3: IFT data of heavy Arabic crude oil with different concentrations of QDECA and QTECA at 25 oC PILs concentrations

QDECA

QTECA

IFT

Ω

IFT

Ω

(mN m-1)

(mN m-1)

(mN m-1)

(mN m-1)

0

33.5

0

33.5

0

0.10

22.5

11.0

25.4

8.1

0.25

15.5

18.0

18.3

15.2

0.50

7.2

26.3

12.1

21.4

0.75

5.3

28.2

10.4

23.1

1.00

3.2

30.3

8.1

25.4

3.4. Demulsification of crude oil water emulsion In the present work, the solvents toluene/ethanol (75/25 Wt %) are selected as mixed solvent for QTECA and QDECA due to the differences in the solubility of the prepared PILs in water. Moreover, these mixed solvents were reported as better diluent for different types of PILs and ILs as demulsifier [18, 19]. The QTECA or QDECA solubilized in toluene/ ethanol ( 30 wt. %) are injected with different concentrations, ranged from 0.1 to 1 g.L-1, into the different crude oil / sea water emulsions as reported in the experimental section. It is used to investigate the effect of QTECA or QDECA concentrations and chemical structures on the demulsification efficiencies of the crude oil water emulsions. The drop test used to determine the continuous phase of crude oil emulsions confirms that all formed emulsions have oil as outer phase. This result elucidates that the formed emulsion may be single phase emulsion as water-in-oil emulsion (W/O) or 24


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Energy & Fuels

multi-phases emulsions as (W/O/W/O). The optical microscopic photos of the crude oil water emulsions is represented in Figure 8 a, which elucidates the formation of multiphase stable emulsions with small drop sizes. The demulsification data included demulsifier efficiencies (η %) and performances (µ; mL min-1) are determined for different crude oil/ water emulsion compositions and listed in Table 4.

A blank demulsification

experiment was conducted by monitoring the separated water and oil without an addition of demulsifier but the equivalent volume of the added toluene/ethanol solvent is added to the controlled sample. The optical microscope photos for crude oil / water separation at different times are represented in Figures 8 b and c. (a)

(b)

(c)

Figure 8. Polarized optical microscope photos of the crude oil/water emulsion (90/10 Vol %) after injection 100 mg .L-1 of QDECA after interval times a) zero , b) 10 and c) 15 minutes.

25


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Page 26 of 38

Table 4: Demulsification data of the crude oil/water emulsions in the presence different concentrations of the prepared QDECA and QTECA at 60 oC.

compounds

QDECA

QTECA

Concentrations (mg.L-1) 10 25 50 100 10 25 50 100

µ mL min-1 0.33 0.013 0.013 0.013 0.666 1.00 0.100 0.063

Crudeoil/water compositions (Vol%) 90/10 70/30 µ µ Time Time η mL mL η% (minute) % (minute) min-1 min-1 100 30 0.150 90 180 0.050 80 120 0.114 80 210 0.089 80 120 0.095 70 220 0.108 240 0.112 80 120 0.075 60 100 15 0.500 100 60 0.233 100 10 0.150 60 120 0.219 60 60 0.107 50 140 0.236 50 80 0.075 40 160 0.238

50/50 η%

Time (minute)

12 32 52 70 56 70 85 100

120 180 240 300 120 160 180 210

The relation between the demulsifier efficiencies and separation times for crude oil/water (90/10 Vol %) using different concentrations of QTECA and QDECA is plotted in Figure 9a and b. The photos for water and oil separations of crude oil / water emulsions are summarized in Figure 10 to show the clarity of the separated water from the residual oil. All demulsification data are recorded at 60 oC using different concentrations of QTECA and QDECA ranged from 10 to 100 mg.L-1. Careful inspection of data listed in Table 4 confirms the decreasing of η % for both QTECA and QDECA with increasing their concentrations above 50 mg.L-1 for crude oil/ water emulsions ( 70/30 and 90/10 Vol %). The η % for both QTECA and QDECA are increased with increasing their concentrations for crude oil water emulsion (50/50 Vol %). Although, lower dosages of QTECA and QDECA demulsifiers show better demulsification performance with low the water content of crude oil water emulsions. The increase of both QTECA and QDECA demulsifier concentrations reduce the water separation of emulsions which referred to the over dosing effects [47]. 26


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Energy & Fuels

Figure 9: Relation between the demulsification time and efficiencies for different concentrations of a) QDECA and b) QTECA of crude oil water emulsion (90/10 Vol %) at 60 oC.

27


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 10. Photos of the crude oil water emulsions a) blank, b) 90/10, c)70/30 and d) 50/50 in the presence of 50 mg. L-1 of QTECA. The demulsification process becomes less cost-effective using higher demulsifier dosage when QTECA and QDECA used in the crude oil / water emulsion (50/50 Vol %) [48]. It is also observed that, the QTECA and QDECA achieve high separation performances and demulsifying action reached 100 % at low concentration 10 mg.L-1 during 30 minutes for crude oil / water (90/10 Vol %) emulsion. The η % data are increased for QTECA demulsifier more than QDECA ( Table 4) when the water content increased in the crude oil water emulsions (50/50 Vol %). The η % values of QDECA are increased more than QTECA at low water content in the crude oil emulsions (90/10 and 70/30 Vol %). Moreover, it is observed that the QTECA has high µ values than QDECA in all different types of crude oil /

28


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Page 29 of 38 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

water emulsions. These data elucidate that the strong ability of QTECA to disperse asphaltene (Figure 6 and Table 2) increases its performance to separate water in short time. Moreover, due to the polar-polar and hydrogen bonding interactions between water and polar groups of QDECA demulsifier, the demulsifier molecules adsorb at the space between droplets and reduce the interfacial barrier to start the water droplet separation as confirmed from Figure 8 b and c, since the oil and water can be separated almost simultaneously.

Moreover, the QDECA acts to flocculate

asphaltenes tend to make the emulsion more stable when the water contents increased in the crude oil/ water emulsion (50/50). The greater ability of QDECA to separate water more than QTECA, but its performance decreased more than QTECA, is referred to its greater ability to reduce the IFT values more than QTECA (Table 3 and Figure 7). The better performance of QTECA more than QDECA can be also related to its chemical structure which contain more hydrophilic hydroxyl groups more than QDECA (Schemes 1 and 2) [49]. These data conclude that the PILs have greater ability to reduce IFT can separate water effectively. Moreover, the PILs have greater tendency to disperse asphaltene perform better as demulsifier than that flocculate asphaltenes. It is great important to meet the specification of water content in crude oil before transporting or entering the refinery plant by removing all water from emulsified crude oil water emulsions. On the other hand, the industry must also consider the residual oil in separated water (i.e. produced water) which becomes wastewater or being used as utilities. The residual oil and water data are determined as reported in the experimental section [50]. A good demulsifier should have the capability to separate water and crude oil with low residue of oil and water in the separated water and crude oil phase, 29


Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 38

respectively. The residual water contents, in the separated oil, obtained by using 10 mg. L-1 of QTECA and QDECA (for crude oil/ water emulsion 90/10) are 972.04 mg L-1 and 1025.90 mg L-1, respectively. These values are in the range of industrial acceptable limit (1000 - 20000 mg L-1). The residual oil contents in the water obtained using 10 mg.L-1 of QTECA and QDECA for crude oil/ water emulsion (90/10) are 72.01 mg L-1 and 225.80 mg L-1, respectively. These data confirm the good ability of both QTECA and QDECA as PILs to act as effective demulsifiers. The existence of residual water in separated crude oil might be due to the formation of microemulsions, which are difficult to destabilize using a purely chemical demulsification process.

4. Conclusions The chemical structure of the hydrophobic cardanol was modified by incorporation of the hydrophilic amines and glycol to obtain new amphiphilic PILs. The surface tension measurements showed that, the QDECA has greater tendency to reduce the surface tension of water more than QTECA. It is referred to the adsorption of QTECA which influenced by cardanol cations. The QTECA anion does not control and significantly affect the adsorption process. The high reduction of the water surface tension for QDECA more than QTECA confirms the weak intermolecular interaction between ions (low zeta potential values) as well as the hydrophobicity of cardanol cations. The good dipole-dipole interaction between sulfonate anion and amine cations of QDECA increases the tighter packing of QDECA at interfaces to increase its concentration by increasing the Г

max

and lowering the Amin to denser arrangement of their cardanol hydrophobic groups. The increasing of asphaltene dispersion efficiencies of QTECA 30


Page 31 of 38 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

more than QDECA can be referred to the adsorption of cardanol positive charges cations on the asphaltene negative charges. The IFT, surface tension and asphaltene dispersion data elucidate that the strong ability of PILs to disperse the asphaltenes in crude oil reduces their ability to reduce the crude oil water interfacial tension. The chemical structure of QDECA is less sterically hindered than QTECA which increases its tendency to irreversibly adsorb at the water-oil interfaces. Hence, the interfacial activity of QDECA increased more than QTECA when they dispersed in the water.

The

demulsification data confirmed that the QTECA and QDECA achieved high separation performances and demulsifying action reached 100 % at low concentration 10 mg.L-1 during 30 minutes for crude oil / water (90/10 Vol %) emulsion. These data concluded that the PILs have greater ability to reduce IFT can separate water effectively. Moreover, the PILs have greater tendency to disperse asphaltene perform better as demulsifier than that flocculate asphaltenes.

Acknowledgment: The authors extend their appreciation to the Deanship of Scientific Research at King Saud University for funding this work through research group No (RGP-235 ). References (1) Liu, G. L.; Xu, X. R.; Gao, J. S. Study on the compatibility of asphaltic crude oil with the electric desalting demulsifiers. Energy Fuels 2003, 17, 543−548. (2) Feng, X.; Mussone, P.; Gao, S.; Wang, S.; Wu, S.-Y.; Masliyah, J. H.; Xu, Z. Mechanistic study on demulsification of water-in-diluted

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Synthesis and Application of Poly(ionic liquid) Based on Cardanol as

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