Synthesis and Application of Amphiphilic Poly(ionic liquid) Dendron

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Synthesis and Application of Amphiphilic Poly (Ionic Liquid) Dendron from Cashew Nut Shell Oil As Green Oilfield Chemicals for Heavy Petroleum Crude oil Emulsion Ayman M. Atta, Mahmood M.S. Abdullah, Hamad A Allohedan, and Amany K Gaffer Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b00165 • Publication Date (Web): 01 Mar 2018 Downloaded from http://pubs.acs.org on March 2, 2018

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Synthesis and Application of Amphiphilic Poly (Ionic Liquid) Dendron from Cashew Nut Shell Oil As Green Oilfield Chemicals for Heavy Petroleum Crude oil Emulsion by Ayman M. Atta1,2,* Mahmood M. S. Abdullah 1, Hamad A. Al-Lohedan1 and Amany K Gaffer 2 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.

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Synthesis and Application of Amphiphilic Poly (Ionic Liquid) Dendron from Cashew Nut Shell Oil As Green Oilfield Chemicals for Heavy Petroleum Crude oil Emulsion by Ayman M. Atta1,2,* Mahmood M. S. Abdullah 1, Hamad A. Al-Lohedan1 and Amany K Gaffer 2 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. Abstract: The green chemicals based on bio-surface active ionic liquids attracted great attention in the petroleum industry due to their high efficiency as multipurposes additives for the petroleum crude oils and their products. In the present work, the chemical structure of the cardanol that produced from cashew nut shell oil was modified and etherified with epichlorohydrine, tetraethylene glycol and ethanolamine to produce branched nonionic surfactants. The amine groups of the cardanoxy ethoxy branches were quaternized and polymerized using 2-acrylamido-2-methylpropane sulfonic to produce dendritic protic ionic liquid. The chemical structure, surface activity, zeta potential and aggregation characteristics of the new modified dendritic nonionic cardanoxy polyphenol and its poly (ionic liquid) in aqueous solution were analyzed and identified. Their applications as


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asphaltene dispersants and demulsifiers for the heavy petroleum crude oil emulsions were investigated to confirm their promising performances. Keywords: Dendron; Poly (ionic liquid); Cardanol; Nonionic Surfactants; Demulsifier; Asphaltene dispersant; Heavy petroleum crude oil.

1. Introduction The crude oil / formation water emulsion occurred during the drilling, production, transportation and storage processes of the crude oils affect their both upstream and downstream operations, specifications and prevent their refining [1-3]. The heavy and super-heavy crude oils are easily emulsified more than light crude oils to form stable water in oil emulsions ( W/O) due to the presence of natural surface active materials based on asphaltenes and resins [2, 3]. There are many serious problems such as corrosion of the petroleum equipment; higher emulsion viscosity that reduced the crude oil pumping during transportation, and refining catalyst poisoning increased the crude oil expenses [4, 5]. The demulsification of the crude oil emulsions using chemicals is an efficient method among several techniques used to solve the emulsion problems such electrical desalting, thermal and mechanical methods (gravimetrical settling and centrifugation) [6-9]. This method based on using nonionic surfactants mixtures based on alkyl phenol, alkyl phenol formaldehyde polymers ethoxylates, ethylene oxide-copropylene oxide polymers, diepoxides and polyesters [10-16]. Recently, ionic liquids (ILs) and modified nanomaterials (such as graphene oxide, titania and magnetite) have been produced to replace the traditional chemicals as effective green oilfield chemicals for different types of crude oil treatments [17-21]. The environmental regulations proposed the replacement of petroleum based surfactants with bio-based surfactants due to 3 ACS Paragon Plus Environment

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their low biodegradability and toxicity that can cause hazardous risk to the ecosystem [22]. The production of an environmentally friendly and effective demulsifiers is still in demand and challenging researchers. Cardanol is a cheap renewable material derived and extracted from the cashew nut shell has been used to produce valuable materials such as nanomaterials and surfactants [23]. In this respect, this study planned to synthesize new biobased nonionic surfactants from cardanol to replace the widely used alkyl phenol ethoxylate derived from petroleum products. Cardanol and polycardanol oil soluble derivatives were used to solve different petroleum problems such as oil spill [24], asphaltene dispersion stabilizer [25, 26], demulsifiers [27], and flow improver and pour point depressants [28, 29]. Its chemical structure was modified to apply as antioxidant for gasoline fuel [30]. Cardanol photoresponsive cationic, gemini conjugated and anionic surfactants showed good results as photoinduced demulsifiers [31, 32]. The chemical structure of cardanol was modified to produce valuable highly surface active materials as nonionic, cationic and anionic surfactants [23, 33]. The modified cardanol polymers were produced from the polycondensation reactions of cardanol either with formaldehyde or polymerization with BF3 [25-27]. These modification methods used toxic reagents and produced non-soluble crosslinked cardanol polymers that cannot used as effective oilfield chemicals. Moreover, these polymers were not active for Arabic heavy crude oil treatment. In this respect, the present work aims to modify the chemical structure of cardanol to produce nonionic surfactants using oxyethylene materials which are more environmentally friendly than formalin and BF3.The branched nonionic surfactants based on 3-pentadecylphenol (cardanol) can be prepared using twosteps. The first step included the addition of phenol to unsaturated 4 ACS Paragon Plus Environment

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double bonds of alkyl substituent of cardanol to produce polyphenols [34]. The produced cardanol polyphenols were etherified with epichlorohydrine, ethanol amine and tretaethylene glycol to modify the hydrophobic skeleton with etherified amine hydrophiles.

The aim of the work extended to

synthesize amphiphilic protic poly (ionic liquid), PIL, by quaternization and polymerization of 2-acrylamido-2-methylpropane sulfonic acid with the prepared cardanol surfactants. The application of the prepared surfactant and PIL as a green bio-based demulsifier and asphaltene dispersant for the Arabic heavy petroleum crude oil water emulsions is another goal of the present work.

2. Experimental 2.1. Materials The chemicals used to modify the chemical structure of cardanol to produce poly (ionic liquids), PILs, were purchased by Sigma-Aldrich chemicals Co., USA. Cardanol extracted from Cashew nut oil was obtained from Shanghai Judong Trading Company Ltd., Chaina). Phenol, ethanolamine (EA), β,βdicholorodiethylether (DCDE), epichlorohydrine (ECH), tetraethylene glycol (TEG) and sodium hydroxide, were used to prepare cardanoxy polyphenol

surfactant.

2-Acylamido-2-methylpropane

sulfonic

acid

(AMPS), 2,2-azobisisobutyronitrile (AIBN) were used to quaternize and polymerize with modified cardanol surfactant to produce PIL. Solvents such as toluene, heptane, xylene and isooctane were used in both synthesis and evaluation of the prepared PIL respectively. Heavy Arabic crude oil (20.8o API), has specific gravity, water, wax and asphaltene contents of 0.929 g.cm-3, 0.145 wt%, 2.3 Wt % and 8.3 wt% 5 ACS Paragon Plus Environment

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respectively, was produced from Ras Tanura wells by Aramco, Saudi Arabia. Its asphaltene fractions were precipitated from the crude oil using toluene: n-heptane solvent as a precipitant with a volume ratio of 1:40 based on ASTM D2007. Its molecular weight determined by gel permeation chromatography (GPC) was 6350 g.mol-1. The sea water was collected from the Arabic Gulf and used to prepare synthetic crude oil emulsions having different crude oil /water compositions (90/10, 70/30 and 50/50 volume %).

2.2. Preparation methods Cardanoxy polyphenol was prepared by heating cardanol (0.1 mol) and phenol (0.2 mol) under rapid stirring at 100 oC in the presence of concentrated sulfuric acid (1 Wt %) for 3 h under N2 atmosphere. The reaction products were extracted by petroleum ether, followed by boiling water distillation to remove the unreacted cardanol, phenol and sulfuric acid. The cardanol polyphenol (0.1 mol) was mixed with excess of ECH (1 mol) and NaOH (0.3 mol; 12 g dissolved in 15 mL of water) under stirring. The reaction mixture was heated and refluxed for 9h under nitrogen atmosphere. The white precipitate NaCl was removed from the reaction mixture by filtration and the excess of ECH was removed by heating the reaction mixture using rotary evaporator. The dark brown product (0.1 mol) was mixed with EA (0.3 mol; 18.3 g) and gently wormed up to 40 oC under N2 atmosphere for 10h. TEG (0.9 mol), DCDE (0.9 mol), toluene (50 mL) and NaOH pellets (1.8 mol) were added to the reaction mixture. The reaction temperature was increased up to 120 oC with stirring the reaction mixture under N2 atmosphere for 6h. The produced NaCl precipitate and the unreacted NaOH were separated from the reaction by filtration. Toluene 6 ACS Paragon Plus Environment

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solvent and the unreacted DCDE were evaporated from the reaction filtrate under pressure using rotary evaporator. The reaction product was mixed with 20 mL of isopropanol and hot aqueous solution of saturated NaCl to salt out the unreacted TEG to water phase. The reaction product was extracted into organic solvent using separatory funnel. The cardanoxy polyether hydroxylamine surfactant was designated as CPEHA and separated as pale brown liquid with reaction yield of 87.3 %. The theoretical and practical nitrogen content were 1.49 and 1.43 (Wt. %), respectively. The purified CPEHA (0.03 mol) was blended and stirred with equimolar of AMPS (0. 03 mol; 0.621 g) and DMF solvent ( 25 mL) for 4h under N2 atmosphere. AIBN (0.1 Wt. % from the weight of AMPS) used as initiator was added to the reaction mixture. The reaction temperature was raised up to 70 oC and kept constant for 24h. The quaternized viscous liquid of cardanoxy polyether hydroxylamine was designated as QCPEA. The reaction yield percentage was 99.8 %. Their S and N contents were determined as 2.38 and 2.10 Wt. %, respectively. 2.3. Characterization of CPEHA and QCPEA The N and S contents of the prepared CPEHA and QCPEA were determined using Carlo Erba 1106 elemental analyzer, and Leco SC 32 sulfur analyzer, respectively according to the procedure ASTM 4239-93. The chemical structures of the prepared CPEHA and QCPEA were determined from Fourier Transform Infrared (FTIR; Nicolet 6700 spectrometer using KBr pellets), 1H and

13

C nuclear magnetic resonance

(NMR; AVANCE 400 Bruker spectrometer using deuterated dimethyl sulfoxide as the solvent).


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Thermal characteristics of CPEHA and QCPEA were evaluated by differential scanning calorimetry (DSC; Shimadzu DTG-60M) and conducted under nitrogen atmosphere at a heating rate of 10 oC per minute. The surface activity and interfacial tension (IFT) of the CPEHA and QCPEA aqueous solutions were determined at room temperature. The pendant drop method using drop shape analyzer (Kruss- DSA-100) was used to determine the surface tension and IFT values of CPEHA and QCPEA in water. Dynamic light scattering (DLS; Zetasizer Nano ZS, Malvern Instrument Ltd., Malvern, UK) was used to determine the aggregations of CPEHA and QCPEA in water, and asphaltenes in the toluene / heptane solvent. The hydrodynamic diameters of the aggregates (Hd; nm) and polydispersity index (PDI) were determined.

The particle sizes Hd and PDI of the

asphaltene dispersion into toluene / n-heptane solvent (asphaltene concentrations 5.0 g L−1 using toluene (1 mL) as asphaltene solvent and nheptane (40 mL) as non-solvent) in the absence and presence the different concentrations of CPEHA or QCPEA were evaluated. The surface charges or zeta potentials (mV) for CPEHA and QCPEA in water contain 0.001 M KCl were determined at 25 °C. The surface charges on the asphaltene were determined by dispersion 1.5 mL of (50 mg of asphaltene in 15 ml ethanol) into 100 ml triply distilled water containing 0.001 M NaNO3 without CPEHA and QCPEA as reference and with different concentrations of CPEHA or QCPEA. Polarized optical microscope (Olympus BX-51 microscope attached with a 100 W mercury lamp) was used to determine the size and shape of the crude oil/ seawater emulsions.


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The relative solubility number (RSN) of CPEHA and QCPEA was determined as mL of water required to obtain turbid solution of the stirred solution CPEHA or QCPEA (2g solubilized in 96mL of dioxane and 4 mL toluene). 2.4. Demulsification of the crude oil sea water emulsions Different compositions of the crude oil sea water emulsions (50/50 to 90/10 Vol %) were prepared as synthetic emulsion using homogenizer at speed 10000 rpm for 30 minute. The CPEHA or QCPEA was diluted with solvent mixture of xylene / ethanol (75/25 Vol. %) to maintain their concentrations at 30 Wt. %. Different concentrations of CPEHA or QCPEA ranged from 10 to 250 mgL-1 were injected into 100 mL of the heated crude oil water emulsions at 60 oC. This temperature was maintained at 60 oC and the time was recorded gradually until the water completely separated from the emulsion. The reference sample of the different crude oil sea water emulsions in the presence of the injected dose based on the solvent (xylene/ethanol; 75/25) and absence of CPEHA or QCPEA was used to determine the emulsion stability in the absence of additives. The demulsification efficiencies (η %) were calculated as η % = Vs/Ve; where Vs and Ve are the separated volume of water at definite time and total emulsified water, respectively. The CPEHA or QCPEA performances ( µ ; mL min-1) were determined as µ = V/t; where V and t are the separated volume of water at definite time and time of separation (minute), respectively. The residual oil in the separated water from demulsification experiment was determined by acidification the water with sulfuric acid to pH (2 to 3), and 9 ACS Paragon Plus Environment

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followed by extraction of the oil twice by 2 mL of isooctane. UV-VIS (PerkinElmer, model Lambda 35) was used to determine the concentration of oil in isooctane at λmax of 255 nm. The residual water in the emulsified crude oil after water separation was analyzed by the Coulometric Karl Fischer titration ASTM-D4928-12 (using a Metrohm Karl Fischer Titrator model 870 KF Titrino Plus).

3. Results and discussion 3.1. Synthesis and characterization of CPEHA and QCPEA Amphiphilic PIL based on cardanol is synthesized by the etherification of cardanol polyphenol produced from reaction of phenol with double bonds of alkyl substituent as represented in schemes 1 and 2. The chemical structure of polyphenol was elucidated as represented in the previous work [34]. The phenol OH groups react with ECH in the presence of NaOH as a catalyst to produce trifunctional cardanoxy epoxides. The formed epoxides react with amine group of EA via aminolysis of the epoxy ring opening mechanism to form cardanoxy alkanol amine as represented in the scheme 1 [35]. The produced hydroxyl and amine groups are etherified with TEG in the presence of DCDE and NaOH as linking agent and catalyst, respectively to produce cardanoxy polyether hydroxylamine surfactant (CPEHA) dendron. The agreement between the theoretical and the practical nitrogen content (reported in the experimental section) confirms the formation of the represented CPEHA chemical structure (Scheme 1). The tertiary amine groups of CPEHA are reacted and quaternized with sulfonate group of the polymerized AMPS (PAMPS) in the presence of AIBN as radical initiator to produce protic ionic liquid dendrimer (QCPEA). The determined sulfur


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content (S %) of QCPEA agrees with the calculated percentage and confirms its chemical structure represented in scheme 2. The chemical structures of CPEHA and QCPEA are confirmed by FTIR and NMR spectra as represented in Figures 1-3. The infrared spectra of the cardanol polyphenol, CPEHA and QCPEA are represented in Figure 1 a-c. The phenolic broad hydroxyl band is observed at 3445 cm-1 in the cardanoxy polyphenol (Figure 1a) was shifted to strong band of 3350 cm-1 for CPEHA (Figure 1 b) to confirm the absence of hydroxyl phenols and formation of ethoxy alcohol groups. The disappearance of vinyl bending vibration bands at 994.7 and 722 cm-1 from all spectra indicates that the phenol reacted with cardanol on C=C bonds of the pentadecyl group. Moreover, the peaks at 780, 695 cm-1 ( referred to C-H phenyl bending of the 1,3-substitution, 827 and 752 cm-1 attribute to the C-H phenyl bending of 1,4- and 1,2- phenyl substitutions, respectively) appeared in all spectra ( Figure 1a-c) elucidate the formation of cardanol polyphenol structure [34]. The appearance of new peak at 3448 cm−1 elucidates the collapse of –NH and –OH of PAMPS amide and TEG, respectively. The new two bands at 1662 and 1613 cm−1 referred to C=O stretching (amide I band) and N–H bending (amide II band), respectively confirm the incorporation of PAMPS in the chemical structure of QCPEA (Figure 1c). The presence of two new peaks at 1379 and 1300 cm−1 (asymmetric and symmetrical stretching of (S=O) group) and the strong stretching absorption in the region of 1089 to 950 cm−1 (represented S–O–C group) in the spectrum of QCPEA (Figure 1c) confirms the presence of sulfonate groups. The interaction between SO3and +NH- groups cannot easily elucidated from their FTIR spectra and it is required using NMR analyses.


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The 1H NMR spectra of CPEHA and QCPEA are represented in Figure 2 a and b. The formation of cardanol polyphenol and the absence of vinyl protons are elucidated from the disappearance of signals between 5 and 6 ppm related to =CH group of pentadecenyl substituent of cardanol. The new signals at 3.41 ppm and 3.78 ppm in the spectra of CPEHA and QCPEA represent the methylene groups of -OCH2CH2 and –N-(CH2)2 , respectively (Figure 2 a). These signals are shifted to 3.49 and 4.15 ppm, respectively due to quaternization of amine groups and formation of amine salt +NH groups of QCPEA ( Figure 2 b) [36]. The disappearance of any signals from 4.5 to 6 ppm and appearance of new signals at 7.45 ppm (–CONH–), 4.4 ppm (–CH2–SO3H), 3.06 ppm (–SO3H), 2.70 ppm (–CH–CO), 2.0 ppm (–CH2–CH–), and 1.42 ppm (–CH3) in the spectrum of QCPEA (Figure 2 b) elucidate the polymerization and contribution of AMPS in the chemical structure of QCPEA. The signal intensities of the methylene and methine groups resulting from the polymerization of PAMPS cannot be measured due to their large broadening and the overlapping with signals of other groups. The broadness of signals at 4.0 ppm elucidates the formation of +NH groups of QCPEA (Figure 2 b). 13

CNMR spectra of CPEHA and QCPEA shown in Figure 3 a and b, are

used for further confirmation of their chemical structures that represented in the schemes 1 and 2. The details for the carbon signals of CPEHA and QCPEA are marked in the spectra of CPEHA (Figure 2a). The appearance of new signals at 164.01, and 52.16 ppm attributed to CONH and C-NH+ of PAMPS in the chemical structure of QCPEA (Figure 3b) elucidates the formation of PIL amine salts with CPEHA of cardanol [37]. The prepared CPEHA and QCPEA are liquid at room temperature and the continuous heating and cooling cycles under nitrogen atmosphere have been 12 ACS Paragon Plus Environment

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carried out to measure their melting (Tm), crystallization temperature (Tc) and glass (Tg) transition using DSC analysis. The DSC thermograms are presented in Figure 4. The QCPEA and CPEHA show low Tm value at 3 and 15 oC, respectively. The QCPEA (Figure 4) shows one Tg at -57.5 oC and CPEHA has not Tg. The low Tg value of QCPEA elucidates better wettability and greater chain flexibility due to quaternization [28]. The CPEHA shows Tc at -42 oC to elucidate its crystallinity with cooling [38]. All these data elucidate the quaternization of QCPEA with PAMPS with forming amorphous poly (ionic liquid).

3.2 Solubility and surface activity The chemical structure of CPEHA (Scheme 1) shows the presence of nonionic hydrophilic oxyethylene units and hydrophobic pentadecyl phenol and polyphenol moieties in their chemical structure. QCPEA (scheme 2) contains ionic sulfonic and quaternized amine groups beside oxyethylene and PAMPS hydrophobic backbone with pentadecyl phenol and bisyphenol moieties. It is expected that the QCPEA and CPEHA behave as surfactants or polyelectrolyte in the aqueous solution. In this respect, the solubility of the prepared QCPEA and CPEHA in water was examined from determination their relative solubility number (RSN) as reported in the experimental section. The RSN value of CPEHA is determined as 13.3 mL of water which reflects its moderate solubility in the water [39]. The RSN value of QCPEA cannot be measured due to its very low solubility into toluene/dioxane solutions. This reflects the low solubility of QCPEA in the mixed solvent that contains high hydrophobic portion (toluene 96 Vol. %) and low hydrophilic portion (dioxane 4 Vol. %). 13 ACS Paragon Plus Environment

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The QCPEA and CPEHA produce a clear solution in water at room temperature. The surface activities of QCPEA and CPEHA in the water solutions are determined at different concentrations to investigate their micellization and adsorption in the bulk solution and at water/air interface, respectively. The relation between their surface tensions (mN.m-1) and their different concentrations (ln c; mol.L-1) is represented in Figure 5. It is observed that, the surface tension of the QCPEA and CPEHA solution decreases with the increase of their concentrations. Their critical micelle concentrations (cmc; mmol.L-1), surface tension at cmc (γcmc) and the slopes of variation of (−∂γ/∂lnc)T are determined and summarized in Table 1. The data show that both QCPEA and CPEHA have the same ability to reduce the water surface tension (γcmc). The QCPEA possesses high cmc and slope value to confirm its higher surface activity more than CPEHA. Moreover, the amphiphilicity of both QCPEA and CPEHA confirmed from their ability to reduce the water surface tension. The QCPEA and CPEHA micelle aggregate sizes or hydrodynamic diameter (Hd; nm) and their polydispersity index (PDI) are determined from DLS measurement and represented in Figure 6 a and b. The zeta potential of QCPEA in water elucidates the formation of a slightly negative -2.12 mV aggregate at pH 7. All these data are used to investigate the solubility and micellization mechanism of both QCPEA and CPEHA in the bulk water solution. The lower both Hd value (139.3 nm) and PDI (0.196) of QCPEA than Hd (578.2 nm) and PDI (0.326) of CPEHA proves the good interaction between cardanoxy polyphenol amine cations and PAMPS sulfonate anions on the exterior surface of micelles and good hydrophobic interaction at the interior surface of micelle as represented in Scheme 3 a. On the other hand, 14 ACS Paragon Plus Environment

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the zeta potential value shows the double electron layer at the QCPEA – water interface exists as negative charge. This charge is produced from the steric hindrance of two oxyethylene branches at amine cations which increases the adsorption of some the PAMPS sulfonate anion on the micelle surface. The repulsive forces between charged micelles reduce the Hd value of QCPEA. Consequently, this proposed micellization mechanism of QCPEA increases its cmc value (Table 1) more than CPEHA. The adsorption of QCPEA and CPEHA at water/air interface is investigated from the calculated surface excess concentration, Г

max,

and the minimum

area of molecules, Amin, at the aqueous–air [40]. The Amin is investigated from the equation: Amin = 1016/ N Гmax, where N is Avogadro’s number. The Г

max

is determined from the following relation: Г

max

= (-∂ γ / ∂ ln c)T /RT.

The data of Гmax, Amin, and (-∂ γ / ∂ ln c) are determined and listed in Table 1. The data of Гmax and Amin of QCPEA and CPEHA are summarized in Table 1. The data confirmed that the presence of the oxyethylene branches in the chemical structure of CPEHA increases its interaction with water at air/water interface. This interaction reduces the concentration of CPEHA and increases its surface area at air/water interface. Moreover, the good dipole-dipole interaction between PAMPS sulfonate anion and amine cations of QCPEA increases its tighter packing at air / water interfaces as represented in Scheme 3b.

This packing increases the QCPEA

concentrations at air/water interface as appeared from its high Г max and low the Amin to denser arrangement of their cardanol hydrophobic groups as represented in the Scheme 3b [41, 42]. The interfacial tension measurements (IFT; mN. m-1) used to describe the ability of QCPEA and CPEHA to adsorb at water/crude oil interface to 15 ACS Paragon Plus Environment

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reduce the crude oil water tension. In this respect, the IFT and Ω data of the heavy Arabic crude oil with water in the presence and absence of QCPEA and CPEHA are determined and listed in Table 2. The data elucidate that the CPEHA reduces the IFT data more than QCPEA. This means that QCPEA behaves as PIL more than surfactants. It is previously reported that, the ILs have low tendency to reduce IFT than the traditional surfactants [43, 44]. The zeta potential data of QCPEA shows its low slightly negative charges, -2.12 mV, that affects its accumulation at water oil interfaces and reduces the IFT [44]. Moreover, it is previously reported the presence of both PAMPS sulfonate anions on the exterior surface of QCPEA micelles and good hydrophobic interaction at the interior surface of micelle assists to form dispersed micelles in water as represented in Scheme 3 a. The great tendency of nonionic CPEHA surfactant to reduce IFT elucidates its ability to arrange their hydrophilic parts in saline water when the crude oil/water replaced the air / distilled water phases [44].

3.3. Interaction of QCPEA and CPEHA with asphaltene The interaction between asphaltene of Arabic heavy crude oil and different concentrations of QCPEA and CPEHA in toluene / n-heptane solutions are investigated using DLS measurements as reported in the experimental section. The Hd and PDI values of the asphaltene agglomerates in toluene / n-heptane solution are determined and listed in Table 3. Their histograms are summarized in Figure 7a-d as representative samples. The data confirm that, the Hd and PDI of asphaltene aggregates are reduced with the increment of QCPEA and CPEHA concentrations. Moreover, the Hd values of QCPEA are reduced more than CPEHA. These data indicate that both QCPEA and CPEHA can act as asphaltene dispersants. The activity of 16 ACS Paragon Plus Environment

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QCPEA increases at its high concentration more than CPEHA. It was previously reported that, the asphaltene charges was changed from the negative to positive based on the dissociation of their acidic surfaces and protonation of basic nitrogen-containing functional groups and adsorption of additives on the asphaltene surfaces [45, 46]. The zeta potential (mV) using different concentrations of QCPEA and CPEHA are determined and summarized in Table 3. The zeta potential of asphaltene determined as -43.3 mV is changed to positive and less negative values (Table 3) with QCPEA and CPEHA, respectively to confirm their adsorption on the asphaltene aggregates. The incorporation of PAMPS in the chemical structure of QCPEA increases the repulsion forces between sulfonate and asphaltene negative charges. The positive and less negative surface charges on the asphaltene increase at high concentrations of QCPEA and CPEHA. It seems to involve the interaction of the PAMPS hydrophobic chain and a hydrophobic surface site of asphaltene. Consequently, the hydrophobic part of the cardanoxy polyphenol of QCPEA is directed to n-heptane to disperse the asphaltene into toluene / heptane solvent. These interactions are greatly increased with increase the sites of QCPEA dendron. On the other hand, the absence of the charges in the chemical structure of CPEHA reduces the charge transfer and electrostatic interactions between CPEHA and asphaltenes, which increase the agglomeration sizes of asphaltene [45]. The good ability of QCPEA to disperse the asphaltene more than CPEHA in the crude oil proposed its application as oilfield chemicals as dispersant and demulsifier [27].

3.4. Demulsification of heavy crude oil water emulsions


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

The previous sections elucidate that, the QCPEA and CPEHA have different characteristics to adsorb or aggregate at interface surfaces and bulk solutions. The micellization and adsorption data (Table 1) of QCPEA and CPEHA aqueous solution confirm that the QCPEA was highly adsorbed and formed dispersed aggregates at air/water interface and bulk water, respectively more than CPEHA in aqueous solution. Moreover, QCPEA was highly adsorbed on the asphaltene surfaces to form dispersed aggregates in toluene/heptane solution (Table 3) more than CPEHA. The IFT data (Table 2) show that CPEHA reduces the interfacial tension between crude oil / water interface more than QCPEA at different concentrations. The reduction of the IFT at crude oil / water interface was referred to the high ability of additives to replace and destroy the viscoelastic asphaltene film at the interfaces to act as demulsifier for petroleum crude oil emulsion [47]. Moreover, the presence of more active sites and branches on the demulsifiers assist to accelerate the asphaltene film thinning rate to increase the demulsification rate [48-50]. On the other hand, it was also reported that, the ILs with long alkyl substituents form elastic films reduce the IFT and disperse asphaltene were used as demulsifiers for the petroleum crude oil emulsion [51, 52]. In the present system, the demulsifier efficiencies (η %) and performances ( µ ; mL min-1), using different concentrations of QCPEA and CPEHA in xylene / ethanol ( 30 Wt. %), are determined for different crude oil/ water emulsion compositions and listed in Table 4. The crude oil / water compositions are ranged from 90 / 10 (Vol %) to 50 / 50 (Vol %) to investigate the effect of emulsion water content as dispersed phase on η % and µ values. The relation between η % and demulsification time using different concentrations of QCPEA and CPEHA for crude oil / water emulsion (90/10 Vol %) is selected and represented in Figure 8 a and b. 18 ACS Paragon Plus Environment

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Energy & Fuels

The polarized optical microscope photos for the selected crude oil / water emulsion (90/10 Vol %) in the absence and presence of QCPEA or CPEHA (250 mg.L-1) are summarized in Figure 9 a-c. The formation of stable crude oil / water emulsions in the absence of QCPEA or CPEHA (reference sample) is confirmed from the zero water separation after heating for two weeks in the presence of the injected dose of xylene / ethanol without demulsifier. The high emulsion stability elucidates from low emulsion particle sizes ranged from 0.8 to 1.8 µm as illustrated in Figure 9 a. The drop test also elucidates that all prepared crude oil water emulsions are dispersed in toluene to confirm that the continuous phase of emulsion is oil to form water in oil (W/O) emulsion as single phase or W/O/W/O multiple emulsion. The demulsification data listed in Table 4 and Figure 8 a show that, the CPEHA does not achieve high demulsification efficiency 100 % even at high concentrations for different crude oil / water emulsions. It is found that, the QCPEA achieves high demulsification efficiency and performance at low concentration for the crude oil / water composition, 90 / 10 Vol %, as represented in Figure 8 b and Table 4. The polarized optical microscope photos for demulsification of crude oil / water composition, 90 / 10 Vol %, in the presence of CPEHA and QCPEA ( Figure 9 b and c) show that the water droplet sizes increase with time and the presence layer of CPEHA surrounded the water droplet ( Figure 9 b). The QCPEA shows different performance with the formation of small aggregates beside the large water droplet (Figure 9 c) to confirm the strong tendency of QCPEA to disperse asphaltene layer surrounded the water droplets faster than CPEHA. Accordingly, the high ability of QCPEA to disperse asphaltene layer surrounded the water droplet increases their performance to act as effective demulsifier for crude oil water emulsion with low water content 19 ACS Paragon Plus Environment

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

(90 / 10 Vol %). The high ability of CPEHA to form flexible layer and to surround water droplet increase the demulsifier performances for crude / oil water emulsion containing more water (50 / 50 Vol %). It was previously reported that, the best branches number of the multi-branched demulsifier to achieve good demulsification performance are ranged from 3 to 5 arms [49]. It was referred to the change of the demulsifier diffusion rate in the continuous phase of emulsions affected the demulsifier to saturate the water / oil interfaces at low concentrations[49]. In the present system, it can be conclude that the presence of PAMPS in conjugation with the quaternized cardanoxy polyphenol amine facilitates the diffusion of QCPEA into the crude oil emulsion with low water content (90/10 Vol %). The low solubility of QCPEA in the crude oil emulsions induces entanglements of the PAMPS chains with a poor diffusion in the heavy crude oil containing more water as dispersed phase [27, 53]. The clarity of water separation which does not contain any contaminated oil is very important environmental target because they converted to wastewater after demulsification. The photos of the water separation of crude oil water emulsions in the presence of CPEHA and QCPEA are summarized in Figure 10 a and b. It is noticed that, the QCPEA shows clear water separation more than that obtained with CPEHA to confirm strong ability of QCPEA to dehydrate micro-emulsion which responsible for oil contaminates in water. This observation can be proved by determination of the residual oil and water as reported in the experimental section. In this respect, the residual oil in water obtained using 250 mg.L-1 of QCPEA and CPEHA for crude oil/ water emulsion (90/10) are 10.01 mg L-1 and 925.30 mg L-1, respectively. Moreover, the residual water in the separated oil using 50 mg.L-1 of QCPEA for crude oil/ water emulsion (90/10 Vol %) is 72.03 mg L-1. These data 20 ACS Paragon Plus Environment

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Energy & Fuels

elucidate the high ability of QCPEA as dendron to demulsify even W/O micro-emulsion with high performances.

4. Conclusions Poly (ionic liquid) dendron, QCPEA, was synthesized from cardanol by the etherification of polyphenol produced from reaction of phenol with double bonds of alkyl substituent followed by quaternization with PAMPS. The thermal properties of QCPEA elucidate the formation of amorphous poly (ionic liquid). The lower both Hd value (139.3 nm) and PDI (0.196) of QCPEA proves the good interaction between cardanoxy polyphenol amine cations and PAMPS sulfonate anions on the exterior surface of micelles and good hydrophobic interaction at the interior surface of micelle. The good dipole-dipole interaction between PAMPS sulfonate anion and amine cations of QCPEA increases its tighter packing at air / water interfaces. High Г

max

and low the Amin increase the QCPEA concentrations at air/water interface to denser arrangement of its cardanol hydrophobic groups. The low tendency of QCPEA to reduce the IFT between crude oil and water elucidates that the QCPEA behaves as PILs more than surfactants.

The interaction data

between asphaltene and QCPEA confirm the incorporation of PAMPS in the chemical structure of QCPEA increases the repulsion forces between sulfonate and asphaltene negative charges. Consequently, the hydrophobic part of the cardanoxy polyphenol of QCPEA is directed to heptane to disperse the asphaltene into toluene / heptane solvent. The good ability of QCPEA to disperse the asphaltene in the crude oil enhances its demulsification results to demulsify the high stable emulsions of heavy crude oil in water (90/10 Vol %) without oil residue in a short demulsification time. 21 ACS Paragon Plus Environment

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Acknowledgment: This project was financially supported by King Saud University, Vice Deanship of Scientific Research, Research Chairs.

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Energy & Fuels

Table 1. Solubility and surface activity data of QCPEA and CPEHA in water at 25 oC. RSN Гmax × Zeta (mL 10 10 γcac ∆γ cac compounds potential (−∂γ/∂lnc)T of µmol/ mmol/L mN/m mN/m (mV) water) m2 CPEHA 13.30 0 0.08 36.82 35.28 10.8 0.044 QCPEA -2.12 0.14 37.22 34.88 18.2 0.0736


Amin nm2 3.77 2.26

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 34

Table 2: IFT data of heavy Arabian crude oil with different concentrations of QCPEA and CPEHA at 25 oC. PILs concentrations

QCPEA

CPEHA

IFT

Ω

IFT

Ω

(mN m-1)

(mN m-1)

(mN m-1)

(mN m-1)

0

33.50

0

33.50

0

0.10

28.50

5.0

21.40

12.1

0.25

24.50

9.0

14.50

19.0

0.50

20.20

13.3

8.30

25.2

0.75

18.30

15.2

3.20

30.2

1.00

13.20

20.3

0.80

32.7

g.L-1


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Energy & Fuels

Table 3: DLS and zeta potential data of asphaltene in toluene/n-heptane and aqueous solutions using different concentrations of QCPEA and CPEHA at 25 oC. Zeta potential

Particle Polymer Polymer

sizes

concentrations

(mV) PDI

(nm) (ppm)

Polymer / asphaltenes

Polymer asphaltenes

CPEHA

QCPEA

100

1149.7

0.321

-20.4

500

1051.7

0.294

1000

631.7

0.212

-4.06

100

1072.6

0.286

15.63

500

981.3

0.165

1000

499.9

0.132

-43.35

-43.35


0

-2.12

-10.5

20.43 26.52

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 32 of 34

Table 4: Demulsification data of the crude oil water emulsions using different concentrations of QCPEA and CPEHA at 60 oC.

Polymer

Demulsification data Conc. (mg.L -1

CPEHA

QCPEA

90/10 η%

)

Time (min)

70/30 µ mL min-1

η%

50/50

Time

η%

(min)

µ mL min-1

Time (min)

µ mL min-1

50

96

360

0.027

84

600

0.042

69.7

630

0.052

100

94

360

0.026

62.0

570

0.033

73.6

600

0.060

250

88

330

0.027

46.7

420

0.033

72.8

600

0.065

50

100

140

0.072

84

540

0.047

48.0

690

0.035

100

100

85

0.118

62

570

0.033

56.0

690

0.041

250

100

75

0.133

46.7

570

0.024

44.0

600

0.036


Page 33 of 34

OH

OH

H2SO4

conc.

OH

100 oC

O

OH O

O O

O

+

CH2

CH2

Cl

NaOH

OH

ECH O

CH2 O

O O

H

H

5

O N

O

O

H

CH2

O

6

CH2

O

O

OH

O O

N

OH

H2NCH2CH2OH

5 H

O

CH2

NHCH2CH2OH

CH2

NHCH2CH2OH

6

H

O

7

H

7 O O

CH2

O N

O O

CH2 OH

H

6

O

5

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

9 ClCH2CH20CH2CH2Cl 9H O OH TEG 4 18NaOH

H

7 H

Scheme 1: Reaction route to prepare CPEHA surfactant.


NHCH2CH2OH

Energy & Fuels

O O

H

H

5

5 O O

H

O H

N O

CH2

O

CH2

6

R

H

O H

+N

6

R O H

O H

7

7

O

CH2

H

O H

+N

6

R

O

O H O

5

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 34 of 34

7 H

O

R=

SO3 N H

PAMPS

Scheme 2: Chemical structure of QCPEA.


Synthesis and Application of Amphiphilic Poly(ionic liquid) Dendron

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