Synthesis, Characterization and Evaluation As Petroleum Demulsifiers of Multi-Branched Block Copolymers

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Article
Synthesis, characterization and evaluation as petroleum
demulsifiers of multi-branched block copolymers.
Edgar I. Hernandez, Laura Verónica Castro Sotelo, Juan Ramon Avendaño-
Gómez, Cesar A. Flores, Fernando Alvarez-Ramirez, and Flavio Vazquez
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b00419 • Publication Date (Web): 03 Jun 2016
Downloaded from http://pubs.acs.org on June 3, 2016
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Page 1 of 54 Energy & Fuels
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3 Synthesis, characterization and evaluation as petroleum demulsifiers of
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6 multi-branched block copolymers.
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a,b b b a
12 E. I. Hernández , L. V. Castro-Sotelo , J. R. Avendaño-Gómez , C. A. Flores , F. Alvarez-
13 a a*
14 Ramírez and F. Vázquez .
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19 a
20 Gerencia de desarrollo de materiales y productos químicos, Instituto Mexicano del Petróleo, Eje
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22 Central (Lázaro Cárdenas), No. 152, San Bartolo Atepehuacan, Delegación Gustavo A. Madero,
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24 D.F., C.P. 07730, MÉXICO.
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27 b
28 Sección de Estudios de Posgrado e Investigación. Escuela Superior de Ingeniería Química e
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30 Industrias Extractivas. Instituto Politécnico Nacional. Av. IPN Nacional s/n, Unidad Profesional
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32 "Adolfo López Mateos", Edificio 8, Tercer piso. México D.F. 07738, MÉXICO.
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44 Corresponding author: fvmoreno@imp.mx
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Energy & Fuels Page 2 of 54
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HIGHLIGHTS:
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10 • Synthesis and characterization of multi-branched block copolymers.
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12 • Theoretical simulation of the synthesis of multi-branched block copolymers by
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14 anionic ring opening polymerization.
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• Demulsification of heavy petroleum.
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3 ABSTRACT
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A series of multi-branched block copolymers was synthetized by means of anionic ring
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8 opening polymerization (AROP) techniques using as initiators different alkoxide salts
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10 obtained from molecules that present different number of alcohol functions. Propylene
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12 oxide (PO) and ethylene oxide (EO) were polymerized in two steps, with the aim of
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14 obtaining multi-branched block copolymers (PO/EO) with demulsifying activity in
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16 petroleum. The characterization of the polymers was done by means of size exclusion
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chromatography (SEC), Fourier transformed infrared spectroscopy (FTIR), carbon-13
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21 nuclear magnetic resonance (13C NMR) and thermogravimetric analysis (TGA). A
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23 theoretical study by semi-empirical AM1/NDDO has been carried out in order to explain
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25 the growing of multiple branches from the initiators during the early stages of the anionic
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27 polymerization. These simulations revealed complex patterns of polymer growth and
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29 increasing polydispersities when initiators with greater number of active sites were
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employed to start the reactions. Afterwards, the water removal efficiency as a function of
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34 the number of copolymer branches was evaluated through bottle tests in two crude oils: a
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36 heavy crude oil with 12.71 °API and an extra-heavy crude oil with 9.68 °API, with a water
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38 content of 47 and 39 vol % respectively. A complex and non-linear behavior of the water
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40 removal as a function of the number of the block copolymers branches was found.
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Keywords: multi-branched polymers, ethylene oxide (EO), propylene oxide (PO), anionic
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47 ring opening polymerization (AROP), dehydrating agents, heavy and extra heavy crude
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49 oils.
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3 INTRODUCTION
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The decrease in worldwide reserves of conventional crude oils and the increase in global
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8 fuel demand have driven forwards innovation in the petroleum industry and spurred on the
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10 development of new production and transportation technologies for heavy crude oils.1
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12 Crude oil is a complex mixture of different and heterogeneous hydrocarbons and when
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14 petroleum is extracted, there is a simultaneous production of water.2,3 Water is normally
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16 present in crude oil reservoirs or injected as steam to stimulate oil production. The
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presence of water in crude oil is undesirable because it undermines the commercial value
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21 of petroleum and the operation of refining equipment. For exporting purposes, crude oil
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23 must contain at maximum 0.5 vol % of water and a salt content lower than 17 511 lb/1000
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25 bbl.4
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27 The emulsification of water in oil is due to the immiscibility between these two liquids, due
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29 to the shear imposed on the fluids during the production flow and to the existence of
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natural surfactant molecules present in petroleum.5 Emulsified water can cause problems
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34 at several stages of the crude oil production, such as: (a) increase of viscosity, (b) higher
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36 cost of transport and storage, (c) corrosion and salt deposits in the refining equipment and
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38 (d) catalyst poisoning.6
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40 The emulsions resulting from this phenomenon are of the water-in-oil emulsion type (W/O),
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42 where relatively stable dispersions of water droplets in crude oil are achieved. Emulsions
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of crude oils are complex systems consisting of sophisticated mixtures of compounds with
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47 different chemical structures.7 Among these compounds, asphaltenes (known as n-
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49 heptane insoluble and toluene soluble fractions, generally distinguished by a fused
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51 aromatic core with polar heteroatom functionalities) contribute mainly to the stabilization of
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53 aqueous dispersions in petroleum. Because of their amphiphilic nature, some researchers
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55 have described that asphaltene molecules create different aggregates above the critical
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58 micellar concentration (CMC) that form highly stable W/O emulsions.7−10
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The methods used to induce phase separation in water-in-crude oil emulsions may be
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8 classified into three main categories: mechanical, electrical, and chemical. Chemical
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10 demulsification consists of the addition of minimal amounts of chemical compounds
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12 (usually 10-1000 ppm) to enhance phase separation rates. It is the most economical and
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14 commonly applied method for dehydrating crude oils.11 Chemical demulsifiers must be
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16 added at an optimal concentration since beyond this emulsion stability can increase again,
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probably due to the formation of a new stabilizing film in which the excess demulsifier
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21 plays a significant role.4
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23 Amphiphilic block copolymers made of a hydrophobic block of polypropylene oxide (PPO)
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25 and a hydrophilic block of polypropylene oxide (PEO) are often employed as demulsifying
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27 agents of petroleum.12 These chemical products are synthesized by anionic ring opening
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29 polymerization (AROP).13 From all the mechanisms of polymerization reactions, the
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anionic mechanism is the only one which provides chemists with and elegant tool for the
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34 synthesis of macromolecules having a remarkable uniformity of chain length, as well as a
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36 predictable molecular weight.14−16 This characteristic feature of anionic polymerization can
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38 also be utilized in the synthesis of block copolymers, branched polymers and terminally
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40 functional polymers, all of which can be controlled to obtain a desired molecular mass
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distribution.17 A living polymerization is a chain polymerization that proceeds in the
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45 absence of the kinetic steps of termination and chain transfer. As mentioned, one of the
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47 unique and important synthetic applications of living polymerization is the synthesis of
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49 block copolymers by sequential monomer addition, permitting complete monomer
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51 conversion.18 In the conventional polymerization process, the anionic polymerization
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53 reaction is initiated by strong bases (such as KOH).19 The synthesis of block copolymers
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starts with the preparation of an alkoxide, which acts as reaction initiator.20 Next, propylene
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58 oxide (PO) is polymerized from the active centers of the initiator and, once the
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3 hydrophobic sequence is finished, ethylene oxide (EO) is made to react and hydrophilic
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chains are formed. Hydroxyl groups are always placed at the polymer chain ends and they
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8 are available for further chemical modifications.4
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10 Hydroxyl terminal groups at the end of polyether chains are responsible for the interactions
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12 at the water/oil interphase, which lead to the coalescence of the aqueous phase, dispersed
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14 in petroleum.21 Consequently, it may be advanced as a hypothesis that a greater number
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16 of end –OH functional groups contribute to a more efficient demulsification process.12 In
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addition, the hydroxyl groups show a very interesting and promising reactive potential,
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21 because they represent a target group for further chemical modifications with a wide
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23 variety of specific substrates.4,20 This makes it possible to obtain a wide variety of
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25 polyethers with improved petroleum demulsifier capabilities. Several studies have been
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27 undertaken in order to elucidate the influence of the number of branches of a surfactant on
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29 its efficiency as petroleum demulsifier and how they can destabilize the water-in-oil
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emulsions formed by the asphaltenes and resins present in the crude oil.21−24 However, a
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34 more systematic study is required, keeping the surfactant HLB (PO/EO ratio) and chain
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36 length constant whilst varying the number of copolymer ends. This would allow a
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38 relationship between the number of branches of a block copolymer and its water removal
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40 efficiency in petroleum to be established.
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In this study, a series of PO/EO block copolymers with one, two, three, four, five and six
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45 arms were prepared by AROP techniques using a group of potassium alkoxides with a
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47 variable number of potential active centers. All these molecules were characterized by
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49 spectroscopic, chromatographic and thermal techniques to ensure that an adequate
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51 polymerization process had been carried out. However, it is very difficult to elucidate if the
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53 PPO chains grow at the same rate from the different active centers in an initiator, so a
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theoretical study was performed in order to determine the uniformity of the arms in a multi-
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58 branched copolymer. Once the preparation of the series of multi-branched copolymers has
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3 been completed, these compounds were dosed in two different heavy crude oils in order to
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experimentally investigate the influence of the number of demulsifier branches on the
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8 removal of water drops dispersed in the petroleum.
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12 EXPERIMENTAL SECTION
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14 Materials.
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16 Reagents: Propylene oxide (PO, 99% purity) and ethylene oxide (EO, 99% purity) were
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18 purchased from Sigma-Aldrich. Tert-butanol (74.12 g/mol), ethylene glycol (62.07 g/mol),
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21 glycerol (92.09), erythritol (122.12 g/mol), adonitol (152.15 g/mol) and D-sorbitol (182.17
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23 g/mol), likewise each of 99 % purity from Sigma-Aldrich, were employed to prepare
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25 initiators. Potassium hydroxide pellets (KOH) (87.1%), HCl (37 wt %/vol) and anhydrous
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27 sodium sulfate (Na2SO4, 99.1%) were purchased from Fermont. Solvents: ethanol,
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29 methanol, hexane, benzene, toluene, xylene, dichloromethane, anhydrous tetrahidrofurane
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(THF), all from Sigma-Aldrich, were used with no further purification.
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36 Synthesis.
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38 a) Alkoxide synthesis. An appropriate amount of multifunctional alcohol was
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40 weighed into a 100 mL balloon flask and a stoichiometric quantity of KOH added in order
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42 to initiate the substitution of the hydroxyl groups by the potassium contra ion and obtain
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the respective alkoxide. A volume of 80 mL of methanol was poured into the flask for
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47 solubilizing all the mixture components. The reacting mixture was put under reflux with
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49 continuous stirring at 80 °C overnight. Once the reaction was complete, ± 90 vol % of
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51 solvent was eliminated using a Dean-Stark trap, in order to maintain in a liquid state the
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53 synthetized alkoxide salt.
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3 b) Procedure of PO homopolymerization. The synthesis of the multi-branched
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copolymers was performed by means of AROP. PO homopolymerization was carried out
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8 at 70 °C; after evaporation of the residual solvent from the initiator system (0.05 mol), the
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10 alkoxide was put in a glass cube placed in a stainless steel Parr© reactor with an
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12 automatic temperature controller. The monomer (100 mL) was loaded into the reactor and
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14 the system was perfectly sealed. Pressure and temperature were controlled until the
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16 reaction finish after 24 h. The PPO was purified by means of a liquid/liquid extraction. For
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this purpose, equal amounts of n-hexane and 0.1 M HCl solution were added to the
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21 polymer. The polymer/solvent mixture was left vigorously stirring for 1 h, after which the
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23 mixture was poured in a separation funnel. Once phase separation was achieved, the
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25 aqueous phase was eliminated and the organic phase dried with anhydrous sodium sulfate
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27 (Na2SO4), filtrated and concentrated under reduced pressure. As homo- and copolymers
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29 were prepared by means of AROP, it was expected that samples with a polydispersity
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index below 1.20 would be obtained; prior literature indicates that this polymerization
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34 method allows chemists to achieve the highest monodispersity of polymer samples.8
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38 c) PO/EO copolymers synthesis proceedure. Copolymerization of the PPO with EO
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40 was carried out at 70 °C in a stainless Parr reactor as described above. The monomer
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42 ratio was PO/EO: 70/30 wt/wt in all cases. For the block copolymer (PO/EO) purification,
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the same procedure employed for homopolymer purification was followed, just replacing n-
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47 hexane by dichloromethane. Further information about the polymerizations (homo- and
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49 copolymerizations) is furnished in the literature.4,21 PO:EO ratio was corroborated by NMR
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51 as described in the Section A of the supplementary information.
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55 Characterization of block copolymers.
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3 a) Fourier transform infrared analysis (FTIR). Infrared spectra were obtained by a
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Thermo Nicolet spectrophotometer, model AVATAR 330 FT-Fourier transform IR equipped
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8 with a DTGS KBr detector. The mathematical treatment of the data was performed with the
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10 OMNIC Version 7.0 software. The liquid polymers were analyzed by film over a NaCl or
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12 KCl window. FTIR spectra were recorded with 64 scans in transmission mode in a
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14 wavelength range of 400 to 4000 cm−1.
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19 b) Carbon-13 nuclear magnetic resonance (13C NMR). Nuclear magnetic resonance
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21 spectra were recorded on a Jeol Eclipse spectrophotometer operating at 300 MHz.
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23 Deuterated chloroform (CDCl3) was employed as a solvent and tetramethylsilane (TMS/Si
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25 (CH3)4) as a reference. In this case, 70 mg of polymer were dissolved in 0.5 mL of
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27 deuterated chloroform.
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32 c) Size exclusion chromatography (SEC). Average molar mass determinations
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34 were performed using a chromatographic system Agilent 1100 Series model comprising:
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36 isocratic pump, a linear column Polymer Laboratories PLgel MIXED-C 5 microns with a
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38 length of 300 mm by 7.5 mm internal diameter. The mathematical treatment of the data
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40 was performed using the Windows MS ChemStation Polymer Laboratories. The SEC
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characterization was carried out using THF as a solvent (instrumental analytical HPLC),
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45 which was pumped at a flow rate of 1 mL/min at 30 °C. In addition, diode array and
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47 refractive index detectors were employed during the analysis. A volume of five µL was
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49 injected in each test. The calibration of the equipment, required to estimate the average
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51 molar masses of the copolymers, was performed using three polystyrene standards from
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Polymer Laboratories-: RED vial = 5000000, 325000, 21000 and 1270 g/mol; BLUE
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56 vial = 1950000, 113300, 7200 and 580 g/mol, GREEN vial = 696500, 50400, 2960
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and 162 g/mol. The numerical values of
, , and polydispersity were determined
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by this technique.
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10 d) Thermo-gravimetric analysis (TGA). TGA analyses were performed on a TGA-
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12 TA Instruments, model 2950; samples between 10 to 20 mg were heated from room
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14 temperature (25 °C) to 500 °C at a heating rate of q = 5 °C/min with a nitrogen flow rate of
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16 10 mL/min. The calibration of the thermal balance with respect to temperature and heat
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flow was carried out using standard samples of calcium oxalate (Aldrich) from room
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21 temperature to 900 °C at a scan rate of 5 °C/min. Calcium oxalate was employed as
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23 standard because its steps of weight loss are clearly defined and separated by
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25 temperature regions where there is no activity and easily quantified by selecting the
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27 beginning and endpoint for each step change.
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Theoretical study of the growth of PPO branches from initiators with multiple active
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34 sites.
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36 The first stages of the polymer branch formation from the polyalcoholates were calculated
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38 in order to establish the main growth tendencies; the PO activation by the active sites of
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40 the initiator and nine subsequent propagation steps were simulated. This theoretical study
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42 was performed by semi-empirical AM1 calculations using the NDDO approach (neglect of
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diatomic differential overlap) implemented in the semi-empirical software package VAMP,
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47 part of Materials Studio (MS version 7.0) from Accelrys, San Diego, CA, USA.25
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51 Heavy crude oils.
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53 Two different Mexican crude oils were employed to test the demulsification efficiency of
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55 multi-branched copolymers: heavy crude oil of 12.71 °API (HCO1) and extra-heavy crude
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oil of 9.78 °API (HCO2). The crude oils were subjected to physical analyses according to
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3 ASTM procedures (API density, ASTM-D-287; Salt content, ASTM-D-3230; Water content,
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ASTM-D-4006; Viscosity, ASTM-D-445; Pour point, ASTM-D-97). These data were
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8 reported in Table 1. Additionally, Table 2 shows the results obtained from SARA analysis
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10 of the crude oils used in the experimental section.
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14 Evaluation of the multi-branched dehydrating agents.
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16 a) Bottle test procedure. Crude oil was poured into a series of graduated bottles with
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18 covers. In each bottle, the petroleum was filled up to the 100 mL graduation. All of the
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bottles were placed in a water bath with controlled temperature at 80 °C for a period of 20
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23 min. An aliquot of the different block copolymers dissolved in xylene (wt/vol concentration)
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25 was subsequently dosed in each bottle, except one (the blank) which was dosed just with
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27 xylene; all the bottles were manual-shaken during 3 min at the rate of 2 beats per second.
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29 After mixing, the dosed bottles were placed again in a thermalized bath at 80 °C and the
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31 rupture of the water-in-oil emulsion was measured during 6 h. The data obtained was
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treated mathematically through Origin Pro 8 and graphs of water removal as a function of
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36 time graphics were plotted.
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38 b) Optical microscopy images. Micrographs of crude oil samples were obtained
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40 through an OLYMPUS microscope, model B201. After finishing the bottle test, a drop of
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42 the crude oil sample dosed with different copolymers was spread over a dust-free glass
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44 slide. Then, the slide was left to dry and was observed by this technique in order to obtain
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images of the heavy crude oils after the dehydrating treatment. The magnification of the
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49 microscope was 100 x and mineral oil was used as a final optimizer in order to facilitate
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51 the visualization of the water drops and to obtain a better image resolution of the W/O
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53 emulsion samples.
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57 RESULTS AND DISCUSSION
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3 Characterization of the heavy crude oils.
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The results from the characterization (physical and SARA analysis) of the two Mexican
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8 crude oils are presented in the aforementioned Tables 1 and 2. Even if their SARA
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10 compositions are similar, these crude oils exhibit very different viscosities. The dissimilar
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12 high contents of water and salt must also be remarked. According to the literature,12 great
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14 amounts of dispersed water and salt significantly reduce the quality of the crude oils
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16 because their processing is very complicated.
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In addition, the content of asphaltenes reported in Tables 1 and 2 is also very great (>10
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21 wt %). As is known, large quantities of these particular petroleum components increase the
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23 emulsion’s stability.21−24
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27 Homopolymer and copolymer synthesis.
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The homopolymers will be identified with the PPO label from 1 to 6, according to the
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32 number of branches they have, meanwhile the block copolymers will be identified with the
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34 PO/EO label from 1 to 6 following the same logic. All polymers were synthesized and
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36 purified with a 95% yield average.
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40 Polymer characterization.
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A spectroscopic characterization of the polymers was performed for all the samples
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45 synthetized, but in order to simplify the interpretation of the data, samples PPO-5 and
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47 PO/EO-5 were selected as representative examples.
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51 Interpretation of FTIR analysis.
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53 Figures 1 and 2 show the most important bands from the PPO-5 and PO/EO-5 samples,
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respectively. In both cases, the principal signal intensities are the following: bands of low
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58 intensity around 3700−3400 cm−1, which indicate the presence of hydroxyl groups, that is,
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60 12
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3 groups belonging to terminal hydroxyl groups (−OH). The signal that appears at about
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6 1115 cm−1 is important since it is the indicative band of the ether´s functionality
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8 (asymmetric tension vibration of the fragment (−C−O−C−) of the aliphatic ether). On the
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10 other hand, the signal that appears from approximately 2990 to 2820 cm−1 corresponds to
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asymmetric and symmetrical tension vibrations of methyl and methylene groups,
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15 confirmed by the flexion band at 1457 cm−1 and the twisting band at 1375 cm−1. It is
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17 important to mention that the band of tension vibration corresponding to the epoxide
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19 fragment is not observed (even from propylene or ethylene oxide functionalities) it should
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have appeared at 3040 cm−1.
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25 13
26 C NMR spectra.
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28 The NMR spectra permit one to compare the signal of a homopolymer (PPO-5) to that of a
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30 copolymer (PO/EO-5). In case of the former, shown in Figure 3, the principal signals from
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32 the three different carbons in the PPO’s structure are indicated by; the signals at 16.98-
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35 18.51 ppm which corresponds to the methyl group (−CH3); the signal at 73.39 ppm, due to
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37 the methylene groups which are bound to the ether (−CH2−O−); whereas the group of
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39 signals between 75.41 and 75.56 ppm belong to the methine groups of the PPO. Finally,
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41 the signal that appears at 59.19 ppm is due to the terminal hydroxyl groups (−CH2−OH).
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44 No signal above 100 ppm was detected, which is evidence that no transfer reactions
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46 interrupted the PO propagation.
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48 On the other hand, on the copolymer´s spectra the peaks that appear at 16.83-18.60 ppm
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50 correspond to the methyl group (−CH3); the signals present at 70.35-70.90 ppm are due to
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the methylene carbons, such as ethylene oxide, as well as propylene oxide (−CH2−O−)
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55 joined by the ether bond; the peaks between 73.41 and 75.17 ppm belong to the methine
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57 carbons of the PPO (Figure 4). The peak shown at 61.73 ppm is due to the carbon joined
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60 13
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3 to the terminal oxhydryl groups of the terminal end chain (−CH2−OH). Again, no signal
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5
6 above 100 ppm was observed, proving that EO propagation was not stopped by side
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8 transfer reactions. Finally, it is worth remarking that the main differences between the
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10 homo- and copolymer spectra is the presence of a signal for the methylene carbon atom of
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12 the EO repetitive unit.
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19 SEC characterization.
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21
The main characteristics of the synthesized polymers, number average molar mass ( )
22
23 and polydispersity index (I), are shown for PO homopolymers (Table 3) and PO/EO block
24
25 copolymers (Table 4).
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27 In the case of homopolymers (denoted as PPO-X in Table 3), alkoxide potassium salts
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29
from the polyalcohols with one, two and three branches allowed for precise control of the
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31
32 molar mass distribution and polydispersity index after polymerization; indeed, low
33
34 polydispersity polymer chains were obtained in these cases. In contrast, copolymers
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36 comprising 4, 5 and 6 branches showed a wide molar mass distribution. Even, when
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38 potassium salts of adonitol and D-sorbitol were employed to start the reaction, 5- and 6-
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40 branched PO homopolymers with a bimodal molar mass distribution were obtained. In
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general, it is observed that the greater the number of potential sites to initiate the
44
45 polymerization, the wider the polymer size distribution.
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47 The subsequent copolymerization of the synthesized PPO chains produced, as expected,
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49 an augmentation of the molecular weight and copolymer branch length, as reported in
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51 Table 4. However, the polydispersity values remained similar. The monomodal or bimodal
52
53 features of the polymers were not affected by the EO grafting on the chain ends.
54
55
56
57
58 Thermal analysis.
59
60 14
1
2
3 The thermogram observed in Figure 5 allows one to establish the interval of thermal
4
5
degradation of the analyzed copolymers. This one goes from 325 to 400 °C; 350 °C can be
6
7
8 considered the average thermal degradation temperature from all the evaluated
9
10 copolymers. Remarkably, these data showed that the copolymers are functional during the
11
12 bottle test, recalling that at the evaluation temperature there is no interference with their
13
14 water removal capability. Furthermore, these molecules will not interfere with the refining
15
16 processes because when they are submitted to temperatures higher than 350 °C,
17
18
complete degradation without solid residues is observed.
19
20
21
22
23 Theoretical study of the polymerization process.
24
25 In this theoretical section, the evolution of the energy associated with the propagation
26
27 stage of PO polymerization was analyzed as a function of the reactive sites in the initiator,
28
29 denoted here by X = 1, 2, 3, 4, 5, 6. The initiator molecule carries a certain number of
30
31
active sites, X, from which different PO branches grow (Figure 6). Because it is not
32
33
34 possible to distinguish experimentally the actual number of branches and their lengths, it is
35
36 necessary to carry out a theoretical energy analysis to know which configurations are
37
38 favored during the first steps of the PO propagation. The modeling of the ethoxylation
39
40 stage was not included in this work because only occurs once the branches are formed
41
42 with sequences of PO structural units.
43
44
A study of the polymeric growth based on conformational energies implies that one needs
45
46
47 to analyze all possible configurations for the same degree of polymerization (Xn, the
48
49 number of structural units in the molecule). For this reason, the energy evolution of the set
50
51 of possible isomers (molecules with the same degree of polymerization) was explored.
52
53 Only the activation stage and the first nine propagation reactions were considered, since at
54
55 this degree of polymerization the growth tendencies of the molecule branches have been
56
57
already expressed. The number of isomers considered in this work depends on the
58
59
60 15
1
2
3 number of reactive sites, X, in the initiator molecule and it tends to grow at a geometric
4
5
rate, making it computationally expensive to carry out this kind of energy study at higher
6
7
8 degrees of polymerization. In Table 5 the relationship between the degree of
9
10 polymerization and the number of isomers analyzed in this research is shown.
11
12 In order to obtain the minimal energy configuration for each of the 14178 molecules
13
14 outlined in Table 5, semi-empirical AM1 calculations were carried out using the NDDO
15
16 approach defined previously. The molecular isomers were assumed to be of neutral
17
18
charge (the OH terminal groups were saturated with potassium atoms to ensure this
19
20
21 neutrality). The structures were completely geometrically optimized allowing a maximum
22
23 gradient of 0.4 kcal/mol/Å and maximum step size of 0.2 Å. The energies of the structures
24
25 obtained at the end of geometrical optimization are going to be used later to discern trends
26
27 of growth through a statistical process of average energy values.
28
29 One way to discern which configuration is favored over another in a set of molecules is by
30
31
the total energy, but this only applies if the set consists of isomers. Meanwhile, in the case
32
33
34 where systems have different numbers of monomers, the energy differences between
35
36 molecules with N and N+1 PO units are small compared to their total energy. An example
37
38 of this is shown in Figure 7, where the energy tendencies are displayed for the case in
39
40 which the initiator contains three potential active sites (potassium glycerolate) and the
41
42 monomer addition goes from 1 to 11 PO units. A linear evolution is observed in the total
43
44
energies of the system as more monomer units, PO, are added to the initiator molecule. A
45
46
47 better way to compare energy values in systems with different degrees of polymerization is
48
49 through their heat of formation; in this way it is possible to distinguish the energy changes
50
51 between polymers with different degrees of polymerization. Figure 7b shows the values of
52
53 the heat of formation of their counterparts displayed in Figure 7a, where a greater
54
55 dispersion of the values is observed when compared with those obtained via the total
56
57
energy, allowing greater differentiation between structures.
58
59
60 16
1
2
3 In isometric systems, i.e. those having the same number of PO units, the most favorable
4
5
configuration is the one with the lowest heat of formation. However, for growth trends, a
6
7
8 measure of how favorable the predisposition is to add a new PO unit to the polymer
9
10 molecule is by determining those transitions that minimize the change in the heat of
11
12 formation from a configuration with i PO units to another with j = i + 1 PO units, denoted
13
14 here as ∆Eij. Thus changes in the heat of formation, ∆Eij, between successive
15
16
polymerization steps were calculated. In particular, in Figure 7c, possible changes to the
17
18
19 heat of formation between successive polymerization steps are outlined for the case of
20
21 potassium glycerolate, with three active sites. Starting from an initial stage in which the
22
23 initiator molecule is the only constituent of the system, the possible routes to lead the
24
25 polymerization from an initial step with zero PO molecules, i, to a final step j, with one PO
26
27 molecule, are indicated with arrows. The energy shifts of these transitions are denoted by
28
29
30 ∆E→ . Similarly, following the polymerization process in the same figure, the change of
31
32 heat of formation change was outlined, but now considering the initial stage to be j = i + 1
33
34

and final stage k = i + 2. In this case, the transitions are denoted as ∆E→. This process
35
36
37 was repeated for the 10 first stages of PO homopolymerization analyzed in this paper,
38
39 resulting in plots of dispersion data that indicate the changes to the heat of formation
40
41 between successive polymerization steps, here simply denoted as ∆E. Figure 7d shows all
42
43 possible heat of formation changes between successive propagation steps from the
44
45 activation of the initiator (stage 0) until largest polymerization stage analyzed in this work,
46
47
10 monomer units. The continuous line represents the average ∆E, denoted ∆E , and
48
49
50 therefore the values of the most abundant energy transitions between successive
51
52 polymerization steps due to the dispersion data shown in Figure 7. In the case of the
53
54 transitions shown in Figure 7d, no distinction was made if the final state of the transition
55
56
57
58
59
60 17
1
2
3 corresponded to an increment of one PO unit in a specific branch, with respect to the initial
4
5
state before polymer growth.
6
7
8 If transitions are distinguished by branches, i.e. considering that the final state of the
9
10 transition involves an increase of one PO unit of a specific branch with respect to the initial
11
12 state, it is possible to build the equivalent of Figure 7d for each of the polymer branches.
13
14 Figure 8 shows the equivalent to Figure 7d in the case of the potassium salt erythritol (four
15
16 active sites), distinguishing the transitions that display a final state increment of one PO
17
18
unit in branch 1 (Figure 8a), branch 2 (Figure 8b), branch 3 (Figure 8c), and branch 4
19
20
21 (Figure 8c) compared to the previous molecule configuration. The dotted curve shows the
22
23 average value of the distribution of transitions shown at the top of each graph.
24
25 It is observed from Figures 7d and 8 that there are two groups of transitions ∆E. In the first
26
27 group are the transitions with ∆E >0, which implies that the heat of formation of the final
28
29 state is greater than that of the initial state. This type of transition, where the number of PO
30
31
32 molecules goes from N to N + 1, are not spontaneous. On the other hand, the second
33
34 group implies ∆E <0 and are spontaneous transitions. In terms of transition rates in
35
36 addition reactions, those reactions with ∆E <0 and greater in magnitude would be more
37
38 energetically favorable. However, because the system exhibits disorder due to entropic
39
40 effects like the presence of solvents and temperature, a greater magnitude transition is not
41
42
always achieved. On the contrary, what most influences the population distribution are
43
44
45 those transitions with ∆E <0 whilst also being the most abundant. In our case, these
46
47 transitions correspond to the average values of the distribution; these correspond to the
48
49 dotted lines in Figures 7d and 8. Therefore, considering that the most abundant transitions
50
51 in the addition process from N to N + 1 PO monomers are those that determine the trends
52
53 in the population distribution, the most likely route of the polymerization process can be
54
55
56
determined from the average values.
57
58
59
60 18
1
2
3 Based on the process described above, it is possible to build from the average values
4
5
curves (dotted lines in Figure 8) the population curve for each of the branches of the
6
7
8 molecule in successive polymerization steps during the first such steps. Figure 9 shows an
9
10 example of the construction of average curves for the case where the starter molecule is
11
12 ethylene glycol (two reactive sites). In Figure 9 one can observe ∆E differences in the
13
14 patterns of the first addition of monomers due to the reduced number of possible isomers
15
16 covered by these early stages, noting that these differences are reduced as the polymer
17
18
grows. A criterion to distinguish which polymer branch grows more than other is assuming
19
20
21 that the growth is governed by the additions in which the average energy is the lowest.
22
23 Based on this, it is possible to outline the most favored growth route between successive
24
25 polymerization stages.
26
27 In particular, for the addition of the first monomer shown in Figure 9, the growth of branch
28
29 1 is slightly favored. In contrast, during step 2 (from 1 to 2 monomers), branch 2 is
30
31
32
energetically favored compared to branch 1. Following the logic of choosing the minimum
33
34 average heat of formation, ∆E , it is possible to graphically describe the energetically most
35
36 favored growth curve according to the polymer images at the top of Figure 9. Following
37
38 this sequence, little difference in growth patterns between the branches 1 and 2 is
39
40 observed. This explains the low polydispersity indices experimentally detected in the case
41
42 of potassium ethyleneglycolate.
43
44
45 Equivalently, Figure 10 reports the growth patterns of the different branches generated by
46
47 the three active sites of potassium glycerolate (PPO-3). In this case, it is evident that
48
49 branches 1 and 3 have stronger growth trends than branch 2, although after adding 10
50
51 structural units of PO the average energy differences are reduced and the propagation
52
53 rate is the same on each branch. It must be emphasized that branch 2 remains the
54
55 shortest of the molecule. Larger differences in growth patterns of the polymer with three
56
57
58 branches, PPO-3, are observed with respect to the polymer with two branches, PPO-2,
59
60 19
1
2
3 resulting in a slight increment in the degree of polydispersity of the polymer chains, as
4
5
revealed by SEC.
6
7
8 Figure 11 shows results of this branch growth analysis for the case of PPO-4 considering
9
10 four potentially active sites of the potassium salt of erythritol. Once the initiator is activated
11
12 and when the first monomer unit is added to the initiator, large ∆E differences and
13
14 subsequent growth patterns are observed. Indeed, it appears that branch 2 is markedly
15
16 favored in the first four stages of propagation of the monomer, whereas the active sites 3
17
18
and 4 hardly experience the addition of further structural units. Arm 1 only shows
19
20
21 intermediate growth from propagation step 5, leading to quasi unidimensional polymer
22
23 growth (∼2 arms). Upon reaching an average degree of polymerization of Xn = 10
24
25 monomeric units, ∆E differences, and consequently propagation rates, are uniform.
26
27 However, only branches 1 and 2 are favored in growth and an almost linear polymer is
28
29
30
generated.
31
32 The potassium salt of erythritol shows major differences in its patterns of growth compared
33
34 with the growth starting from initiators with two or three active centers. The salt shows
35
36 larger changes in its growth because the propagation from reactive sites 2 and 1 are more
37
38 highly favored. This causes a greater distribution of molecules with different growths,
39
40 which results in greater polydispersity of the polymer synthesized with 4 limbs.
41
42
43
For the initiator with five active sites, the branch growth pattern shows a more
44
45 differentiated behavior with respect to the previous cases (Figure 12). In the early stages
46
47 of monomer addition to the initiator, only two of the arms (2 and 5) display a continuous
48
49 average growth. Surprisingly, from the stage with four PO monomers, branch 5 shows
50
51 marked growth. This implies that only a few of the isomers in the distribution of polymers
52
53 present growth on reactive sites 1 to 4. This explains why the polymers with five branches
54
55
56
show two bimodal populations; the first peak of the bimodal molar mass distribution
57
58
59
60 20
1
2
3 corresponds to the very fast growth of branch 5 in the molecule, and the second peak can
4
5
be associated with molecules having branches that are lagging behind in their growth.
6
7
8 Figure 13 shows the largest ∆E during polymerization, implying a greater number of
9
10 possible patterns of growth, branch 5 being markedly the most favored. However, after the
11
12 addition of 9 PO monomeric units these differences disappear and simultaneously
13
14 propagation rates become constant. The reactivity differences between the initiator sites
15
16 results in greater variety of isomers with very different branch lengths. This is observed
17
18
experimentally as a very broad and bimodal distribution of molar masses detected by SEC.
19
20
21 Thus, the AM1/NDDO simulations demonstrate that using initiators with a higher number
22
23 of active sites for AROP means that the number of possible growth patterns increases,
24
25 which directly impacts the polydispersity of synthesized polymers.
26
27
28
29 Water removal efficiency.
30
31
32
The results of the bottle test obtained by dosing 500 and 1000 ppm in HCO1 (12.71 °API)
33
34 are reported in Figures 14 and 15, respectively. The block copolymer with two branches
35
36 worked better at 500 ppm, breaking the emulsion after just a few minutes, quickly
37
38 coalescing the water droplets. One should note that this dehydrating agent is made of
39
40 linear chains of the lowest molecular weight (just 2058 g/mol).4 The copolymers prepared
41
42 from initiators with four and five reactive sites induced emulsion breaking after a few
43
44
45
minutes, removing water from the emulsion at a high rate. This behavior may be correlated
46
47 to the fact that only two branches tend to grow from the initiator, which means that they
48
49 present some structural similarity to PO/EO-2. In contrast, the copolymer with six irregular
50
51 branches, PO/EO-6, required more time to break the emulsion and remove the water in
52
53 the petroleum. The copolymers with one and three branches showed a poor capacity to
54
55 eliminate the dispersed water.
56
57
58
59
60 21
1
2
3 The behavior of the multi-arm copolymers is completely modified when their dose in
4
5
petroleum is increased to 1000 ppm. The first unexpected result is the loss of demulsifier
6
7
8 efficiency of the two-branched copolymer. In spite of the fast emulsion breaking induced by
9
10 this dehydrating agent, a drop in its coalescence capability could observed. The two-
11
12 branched copolymer could remove only 65 vol % of the dispersed water from the
13
14 petroleum. A possible explanation for this phenomenon is a saturation of the water/oil
15
16 interface by the two-branched chains. In contrast to the poor results observed at a dose of
17
18
500 ppm, the copolymers with one and three branches showed a greater capability to
19
20
21 remove the emulsion at 1000 ppm, perhaps due to the higher concentration gradient
22
23 allowing improved diffusion through the crude oil. This diffusion may also be promoted by
24
25 a suitable molecular weight, near 2000 g/mol, similar to that of PO/EO-2.4 Both copolymers
26
27 started to separate water from the crude oil almost instantaneously and stimulated a fast
28
29 coalescence rate until reaching complete water removal.
30
31
The polymers with 4 and 5 ends also provoked an instantaneous emulsion destabilization,
32
33
34 followed by a fast coalescence of the water droplets. However, only 85 vol % of the
35
36 dispersed water could be extracted from the petroleum.
37
38 The large molecules comprising six branches did not show any dehydrating capability.
39
40 This disappointing result can be explained in terms of a less solubility of these heavy
41
42 molecules in petroleum, which induces entanglements of the polymer chains and a poor
43
44
diffusion in the heavy crude oil.4,26,27 A theoretical study of the loss of demulsification
45
46
47 efficiency of a dehydrating polyether when its average molecular mass is increased upon
48
49 an optimal value has been reported elsewhere.28
50
51 When the multi-branched copolymers were evaluated in the second sample of heavy
52
53 crude oil (9.68 °API), the greatest efficiency of the molecule consisting of two branches
54
55 was observed once again at 500 ppm (Figure 16). However, a maximal water separation
56
57
of only 85 % was achieved at these conditions. As in the previous case, a fall of the
58
59
60 22
1
2
3 demulsification activity of the two-branched polymer was observed when the applied dose
4
5
was doubled (Figure 17). The time until water separation started increased to 107 minutes
6
7
8 and a maximal removal of the aqueous phase of 90 vol % was finally reached. A possible
9
10 explanation of the reduced dehydrating capability of the polymer with two branches is also
11
12 that of a saturated water / oil interface.
13
14 In contrast, all the remaining copolymers showed very weak demulsification activity. Only
15
16 the very large molecules with six branches allowed 32 vol % separation of the water n
17
18
dispersed in the heavy petroleum.
19
20
21 With the exception of the two-branched molecule, when the concentration of the
22
23 copolymers was increased to 1000 ppm, their diffusion thorough the oil phase increased
24
25 and their dehydrating activity was revealed. Indeed, a progressive dewatering efficiency
26
27 was clearly observed when the number of branches increased. Copolymers comprising
28
29 four, five and six ends immediately started to break the emulsion. A maximal water
30
31
removal of 83 vol % was attained for such multi-branched polymers.
32
33
34 After analyzing the full set of data, a non-linear correlation was found between the number
35
36 of branches and the water removal efficiency; this can be explained in terms of the
37
38 complex morphology of copolymers with a greater number of branches.
39
40 It is valid to state that the demulsifing capability of the multi-branched copolymers is dose-
41
42 dependent, meaning that their efficiency is strongly related to the concentration added to
43
44
the crude oil sample. How it could be expected, the lower concentration of the applied
45
46
47 demulsifier in the crude oil, the more possibilities to use these products at industrial level.
48
49 The traditional two-end block copolymers were found to show excellent dewatering activity
50
51 at low concentration in this study.
52
53 It is noticed that the water separated percentage is different in all the cases (Figures 18
54
55 and 19). The differences can be explicated by means of the complex mechanism of the
56
57
water removal phenomenon, which comprises three principal stages:5
58
59
60 23
1
2
3 a) the rate of diffusion which comprises the migration of the dehydrating agent to
4
5
the interface of the water drops, stabilized with asphaltene-resin layers,6,18 in order to
6
7
8 increase the interfacial tension and promote the water drop’s release and coalescence;
9
10 b) the water removal rate, directly related to the rate of diffusion, which is the time
11
12 the molecule (dehydrating agent) takes to destabilize the water-asphaltene/resins complex
13
14 and break down the water-in-oil emulsion of the heavy crude oil; the faster the water is
15
16 removed from the petroleum, the greater the efficiency of the dehydrating agent;
17
18
c) the water clarifying effect, where the water is cleaned up from most of the
19
20
21 components of the heavy crude oil, meaning there is no or only a minimal trace of
22
23 hydrocarbon present in the water phase.
24
25
26
27 In the case of the demulsifiers that have one, two and three branches (Figures 18 and 19),
28
29 the water phase shows, in all case, some “dirtiness”; some petroleum components left in
30
31
the water phase for both crude oil samples (HCO1 and HCO2). It means that the
32
33
34 dehydrating agents do not completely clarify the water requiring further treatment to do so.
35
36 In contrast, the three aforementioned phenomena were detected in petroleum samples
37
38 dosed with 1000 ppm of the demulsifiers consisting of 4 and 5 branches. These multi-
39
40 branched copolymers can diffuse quickly into the crude oil, in order to increase the
41
42 demulsification process, and as well as exhibiting a better clarifying effect on the removed
43
44
water (Figure 18 and 19). In the specific case of HCO1 crude oil dosed with the five-
45
46
47 branched block copolymer, despite is the presence of some crude oil on the walls of the
48
49 bottle, the water phase seems clear, similar to HCO1 dosed with the four-branch
50
51 copolymer. This is in stark contrast to the water phases obtained from the petroleum
52
53 sample containing copolymers with a low number of branches (1 to 3) and those extracted
54
55 from HCO1 dosed with demulsifiers of a greater number of branches (4 to 6). In spite of its
56
57
58
59
60 24
1
2
3 greater number of branches, the six-branched copolymer did not show any dewatering
4
5
capability in this crude oil.
6
7
8 The results obtained after the evaluation of the block copolymers with 4, 5 and 6 branches
9
10 in the HCO2 crude oil (Figure 19) showed the best water clarification and, as discussed
11
12 above, the three phenomena involved in the demulsification action (emulsion breaking,
13
14 drop coalescence and clarification) had clearly occurred when these samples were applied
15
16 to the petroleum. The water appears distinctly clearer in these cases than when a smaller
17
18
number of branches (one, two or three) were used.
19
20
21
22
23 Optical microscopy.
24
25 Some optical micrographs were taken of the W/O emulsions in order to corroborate the
26
27 results obtained by the bottle test. The images of HCO1 and HCO2 emulsions treated with
28
29 the polyether with five branches are shown as examples. The same dehydrating behavior
30
31
was observed in both crude oils.
32
33
34 In Figure 20a, an image of the water dispersed in the heavy crude oil HCO1 (12.71 °API)
35
36 with no further treatment is shown; a large number of droplets, corresponding to water
37
38 content of 39 vol %, is easily seen. Figure 20b shows a sample after the dehydrating
39
40 treatment (water removal of 82 vol %, t = 300 min), where the little spheres in the picture
41
42 are the remaining water drops from the broken down water-in-oil emulsion in the HCO1
43
44
sample; the drop sizes are bigger than in the previous micrograph because of drop
45
46
47 coalescence induced by the demulsifier. Figure 20c is an image of a sample after 100 vol
48
49 % of water content removal. The difference could also be appreciated by the coloration
50
51 change in each case; as more water is lost, a maroon color is observed due to the nature
52
53 of the chemical compounds contained in the crude oil.
54
55 Figure 21 shows the equivalent process with crude oil HCO2. Firstly, with no further
56
57
treatment is shown in Figure 21a); the principal difference of this image compared to the
58
59
60 25
1
2
3 micrograph of Figure 20a is that the water content is larger (47 vol %) than in the case of
4
5
HCO1 crude oil sample. Consequently, Figure 21b) shows a sample after the dehydrating
6
7
8 treatment (62 vol % of water removal), where the larger spheres in the micrograph are due
9
10 to the coalescence of water droplets; in this case the drops look larger than in Figure 20b
11
12 because of the higher content of water and lower water removal. Finally, Figure 21c) is the
13
14 image of a HCO2 sample after having removed 100 vol % of the water content; the same
15
16 behavior is observed as for HCO1.
17
18
19
20
21 CONCLUSIONS
22
23 A series of multi-branched copolymers were synthesized by means of the anionic
24
25 polymerization of PO and EO started with initiators of polyalkoxide type. A
26
27 physicochemical characterization of the synthesized molecules was performed, observing
28
29 that the polydispersity increases with the number of potential polymerization sites of the
30
31
initiator. Alkoxides with five and six potential reactive sites generated very polydisperse
32
33
34 polymers with a bimodal molar mass distribution. However, polymer distributions of
35
36 molecules with one, two and three branches detected by SEC displayed a low
37
38 polydispersity value of 1.20.
39
40 The theoretical simulation revealed irregular and complex patterns of growing for polymers
41
42 consisting of four, five and six branches. Whereas copolymers with one, two and three
43
44
branches consist of more or less equal molecules, the copolymers with more than three
45
46
47 branches present a greater variety of different isomers with arms of different lengths. The
48
49 irregularity of the growing patterns detected in molecules with a greater number of
50
51 branches can be attributed mainly to steric hindrance, which avoids that monomer units
52
53 could approach to each active site. Furthermore, the addition of monomers is carried out
54
55 by the side with less hindrance. This behavior is more evident when the initiator has more
56
57
reactive sites.
58
59
60 26
1
2
3 The demulsification of heavy crude oils with multi-branched copolymers revealed a very
4
5
complex and non-linear dependence of the dehydrating efficiency with the number of
6
7
8 polyether branches, mainly as consequence of the complex patterns of growth developed
9
10 when the number of initiation sites increases. Moreover, although in theory the increment
11
12 of the number of demulsifier branches favors interphase destabilization, one must
13
14 simultaneously take into account that this molecular parameter makes the diffusion of the
15
16 demulsifier through the crude oil more difficult.
17
18
It must also be remarked that for the two samples of heavy crude oils that received a low
19
20
21 dose of 500 ppm, the traditional two-branched copolymer promoted fast emulsion breaking
22
23 and drop coalescence. Likely, the optimal performance of this copolymer at this
24
25 concentration is due to a complete covering of the water/oil interface.4 If the dose of the
26
27 two-branched copolymer is increased upon this concentration, a loss of their dehydrating
28
29 capacity is observed. However, this subject is still open to new research.
30
31
On the other hand, the water clarification properties at the same dose (500 ppm) of the
32
33
34 five-branched copolymer must also be highlighted. A formulation combining two- and five-
35
36 branched copolymers could provide an excellent option for the demulsification of heavy
37
38 crude oils.
39
40
41
42 AUTHOR INFORMATION
43
44
Corresponding author. *Telephone: +52-55-9175-8402. Email: fvmoreno@imp.mx
45
46
47
48
49 Acknowledgement: useful assistance of Alfonso López Ortega in synthesis and
50
51 characterization of copolymers is gratefully acknowledged.
52
53
54
55
56
57
58
59
60 27
1
2
3 REFERENCES
4
5
(1) dos Santos, R. G.; Bannwart, A. C.; Briceño, M. I.; Loh, W. Chem. Eng. Res. Des.
6
7
8 2011, 89, 957−967.
9
10 (2) Castro, L. V.; Vazquez, F. Energy Fuels, 2009, 23, 1603−1609.
11
12 (3) Chatila, S.G. Evaluation of Crude Oils. In Petroleum Refining, Vol. 1; Crude Oil;
13
14
Wauquier, J.-P., Ed.; Editions Technip: 2000; pp 326−330.
15
16
17 (4) Cendejas, G.; Arreguín, F.; Castro, L. V.; Flores, E. A.; Vázquez, F. Fuel, 2013, 103,
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19 356−363.
20
21 (5) Peña, A. A.; Hirasaki, G. J.; Miller, C. A. Ind. Eng. Chem. Res., 2005, 44, 1139−1149.
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23
24
(6) Filho, D. C. M.; Ramalho, J. B. V. S.; Spinelli, L. S.; Lucas, E. F. Colloids Surf., A,
25
26 2012, 396, 208−212.
27
28 (7) Becker, J. R. Crude oil. Waxes, emulsions, and asphaltenes, PennWell: Tulsa, OK,
29
30 1997.
31
32 (8) Rondón, M.; Bouriat, P.; Lachaise, J.; Salager, J. L. Energy Fuels, 2006, 20,
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35 1600−1604.
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37 (9) Rondón, M.; Pereira, J. C.; Bouriat, P.; Garcia, A.; Lachaise, J.; Salager, J. -L. Energy
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39 Fuels, 2008, 22, 702−707.
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41 (10) Borges, B.; Rondón, M.; Sereno, O.; Asuaje, J. Energy Fuels, 2009, 23, 1568−1574.
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44 (11) Pacheco, V. F.; Spinelli, L.; Lucas, E. F.; Mansur, C. R. E. Energy Fuels, 2011, 25,
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46 1659−1666.
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48 (12) Zhang, Z.; Xu, G.; Wang, F.; Dong, S.; Chen, Y. J. Colloid Interface Sci., 2005, 282,
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50 1−4.
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(13) Maurice, M. Anionic polymerization: principles and practice; Academic Press Inc.,
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55 London, 1983.
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60 28
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3 (14) Quirck, R. -P., Applications of anionic polymerization research; American Chemical
4
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Society, Orlando, FL, 1996.
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8 (15) Šutinská, V.; Pajtášová, M.; Ondrušová, D.; Ľalíková, S.; Ferjancová, A.; Paliesková,
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10 J.; Mojumdar, S. C. J. Therm. Anal. Calorim. 2011, 104, 923−927.
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12 (16) Gervais, M.; Brocas, A. -L.; Deffieux, A.; Ibarboure, E.; Carlotti, S. Pure Appl. Chem.
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14 2012, 84, 2103−2111.
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17 (17) Carlotti, S.; Desbois, P.; Warzelhan, V.; Deffieux, A. Polymer, 2009, 50, 3057−3067.
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19 (18) Cendejas, G.; Flores, C. A.; Huitrón, N.; Herrera, R.; Zamudio L. S.; Beltrán, H. I.;
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21 Vázquez, F. J. Mol. Struct., 2007, 879,40−52.
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23 (19) Cendejas, G.; Arreguín, F.; Flores, C.; Villalobos, I.; Flores, E.; Vázquez, F. Catal.
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26 Today, 2008, 130, 486−491.
27
28 (20) Cendejas, G.; Flores E. A.; Castro, L. V.; Estrada, A.; M. Lozada; Vázquez F.
29
30 Demulsifying and dehydrating formulations for heavy crude oils based on block
31
32 copolymers bifunctionalized with amines. US Patent 8,815,960B2, August 26, 2014.
33
34 (21) Spiecker, P. M.; Gawrys, K. L.; Trail, C. B.; Kilpatrick, P. K. Colloids Surf., A, 2003,
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37 220, 9−27.
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39 (22) Pereira, J. C.; Delgado-Linares, J.; Scorzza, C.; Rondón, M., Rodríguez, S.; Salager,
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41 J. -L. Energy Fuels 2011, 25, 1045−1050.
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43 (23) McLean, J. D.; Kilpatrick, P.K. J. Colloid Interface Sci. 1997, 189, 242−253.
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46 (24) Papirer, E.; Bourgeois, C.; Siffert, B.; Balard, H. Fuel 1982, 61, 732−734.
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48 (25) Clark, T.; Alex, A.; Beck, B.; Burkhardt, F.; Chandrasekhar, J.; Gedeck, P.; Horn, A.
49
50 H. C.; Hutter, M.; Martin, B.; Rauhut, G.; Sauer, W.; Schindler, T.; Steinke, T.; VAMP 8;
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52 Accelrys Inc Erlangen, San Diego, 2003−2005.
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55 (26) Mansur, C. R. E.; Barboza, S. P.; González, G.; Lucas, E. F. J. Colloid Interface Sci.
56
57 2004, 271, 232−240.
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59
60 29
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3 (27) Rodrigues-Ferreira, S.; Ferreira-Louzada, H.; Moyano–Dip, R. M.; González G.;
4
5
6 Lucas E.F., Energy Fuels, 2015, 29, 7213−7220.
7
8 (28) Álvarez, F; Flores, E.A.; Castro, L.V.; Hernández, J.G.; López A.; Vázquez, F., Energy
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10
Fuels, 2011, 25, 562−567.
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60 30
1
2
3 TABLES
4
5
6
7 Table 1. Physical features and properties of crude oils submitted to dehydrating tests.
8
9 Physical analysis
10
11 Crude oil Density Salt Water Kinematic viscosity Pour point
12
2
13 (°API) (lb/1000 bbl.) (vol %) @ 25 °C (mm /s) (°C)
14
15 HCO1 12.71 17296 39 1636 −6
16
17 HCO2 9.68 20042 47 4650 −12
18
19
20
21 Table 2. SARA analysis of the crude oils employed to evaluate multi-branched block copolymers.
22
23 SARA analysis
24
25 Crude oil Saturated Aromatics Resins Asphaltenes
26
27 (wt %) (wt %) (wt %) (wt %)
28
29 HCO1 2.31 4.56 81.18 11.93
30
31 HCO2 2.44 6.59 78.35 12.59
32
33
34
35
Table 3. Polypropylene oxide (PPO) homopolymers synthetized by AROP (T = 70 °C, [Initiator]t=0 =
36
37
38 0.5 M, x ≈ 99 %).
39
40 ID
(g/mol) I
41
42 PPO – 1* 1697 1.10
43
44 PPO – 2 1568 1.14
45
46 PPO – 3 1655 1.17
47
48 PPO – 4 2650 1.25
49
50 PPO – 5 3600, 1044 1.02,1.13
51
52 PPO – 6 10300, 1980 1.03, 1.18
53
54 * The number in the label indicates the number of homopolymer branches
55
56
57
58
59
60 31
1
2
3 Table 4. Block copolymers obtained after ethoxylation of PPOs. In all cases, the ratio of propylene
4
5 oxide and ethylene oxide is PO/EO: 70/30 wt/wt.
6
7 ID
I
(g/mol)
8
9
PO/EO – 1* 2230 1.14
10
11
PO/EO – 2 2058 1.18
12
13 PO/EO – 3 2164 1.18
14
15 PO/EO – 4 3465 1.29
16
17 PO/EO – 5 5060, 1632 1.02,1.09
18
19 PO/EO – 6 14250, 3030 1.03, 1.13
20
21 *The number in the label indicates the number of copolymer branches
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 32
1
2
3
4
5 Table 5. Number of isomers as a function of the degree of polymerization used for the energy
6
7 analysis of the PO propagation.
8
9 Potassium salt
10 Potassium salt Potassium salt Potassium salt Potassium salt
11 Initiator of ethylene
12 of glycerol of erythritol of adonitol of sorbitol
13 glycol
14
15 Number of
16 2 3 4 5 6
17 reactive sites
18
19 Number of
20 77 363 1364 4367 8007
21 isomers
22
23 PO addition 1 2 3 4 5 6
24
25 PO addition 2 3 6 10 15 21
26
27 PO addition 3 4 10 20 35 56
28
29 PO addition 4 5 15 35 70 126
30
31 PO addition 5 6 21 56 126 252
32
33 PO addition 6 7 28 84 210 462
34
35 PO addition 7 8 36 120 330 792
36
37 PO addition 8 9 45 165 495 1287
38
39 PO addition 9 10 55 220 715 2002
40
41 PO addition 10 11 66 286 1001 3003
42
43 PO addition 11 12 78 364 1365 --
44
45 Total number of analyzed isomers = 14178
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 33
1
2
3 FIGURES
4
5
6
7
8
9
10
11
12
13
1 00
14
15
16 90
17
18 80
19
(-OH)
3489
20 70
21
22 60
23
%T
24 50
25
26 40
HO
O m
IN
O m
OH
27
28
1460
865
1339
30
29
30 20
31
2964
2860
2929
32
918
1371
10
33
34 -0 1100
35 4 000 3 500 3 000 2 500 2 000 1 500 1 000 5 00
36 c m -1
37
38 Figure 1. FTIR spectrum of a homopolymer sample: PPO-5 (IN: initiator).
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 1
1
2
3
4
5
6
7
8
9
10 1 10
11
12
1 00
13
14
90
15
3470
16
80
17
Increase of
18
70 the aliphatic
19
signal
20
60 intensity.
21
%T
22
23 50
24
25 40
26
2970
27 30
1453
28
1341
29 20
841
30
1371
31
924
10
2869
32
33 0
34 1100
35 4 000 3 500 3 000 2 500 2 000 1 500 1 000 5 00
36 c m -1
37
38 Figure 2. FTIR spectrum of copolymer sample PO/EO-5. In this case, the difference
39
40
between the homopolymer and the copolymer is the signal increase corresponding to the –
41
42
43 CH2– groups in the molecule.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 2
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 Figure 3. Representative 13
C NMR spectrum (PPO-5) shown in order to elucidate the
44
45
structure of the homopolymer samples (IN: initiator).
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 3
1
2
3
4
5
6
7
8
9
10
11
12
13
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15
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17
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19
20
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23
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25
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27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Figure 4. Representative spectra shown in order to elucidate the structure of the samples.
46
47 13
48 C NMR spectra of the PO/EO-5 block copolymer (IN: initiator).
49
50
51
52
53
54
55
56
57
58
59
60 4
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 110
17 100 PO/EO - 3
18
90
19 PO/EO - 1
20 80 PO/OE - 4
PO/OE - 6
PO/EO - 5
21
Weight loss (wt %)
70
22 PO/OE - 2
60
23
24 50
25 40
26 30
27
20
28
29 10
30 0
31 -10
32 -50 0 50 100 150 200 250 300 350 400 450 500 550
33 Temperature (°C)
34
35
36
37 Figure 5. Thermograms of the multi-branched copolymers employed as crude oil
38
39 demulsifiers (q = 5 °/min).
40
41
42
43
44
45
46
47
48
49
50
51
52
53
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59
60 5
1
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8
9
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17
18
19
20
21
22
23
24
25
26
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29
30
31
32
33
34
35
36
Figure 6. Structure of anions derivatives of: (a) tert-butanol; (b) ethylene glycol, (c) glycerol;
37
38 (d) erythritol, (e) adonitol and (f) sorbitol.
39
40
41
42
43
44
45
46
47
48
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57
58
59
60 6
1
2
3
4
5
6
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24
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26
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30
31
32
33
34
35
36
37
38
39
40
41 Figure 7. Energy evolution in terms of degree of polymerization PO of the initiator for the
42
43 case of three possible active sites (potassium glycerolate): (a) total energy, (b) heat of
44
45 formation, (c) examples of possible routes of spread of PO between the steps i, j and k; (d)
46
47 differences between the heat of formation between successive polymerization stages i and
48
49 j. The continuous line represents the average energy change.
50
51
52
53
54
55
56
57
58
59
60 7
1
2
3
4
5
6
7
8
9
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30
31
32
33
34
35
36
37
38
39
40
41
42
43
44 Figure 8. Distribution of heat of formation changes, E, between successive stages of PO
45
46 monomer addition for the case of erythritol. (a) branch 1, (b) branch 2, (c) branch 3 and (d)
47
48
49 branch 4. Illustrated at the top of each graph as a bar chart is the distribution of the dispersion
50
51 data plotted in (a-d). Figures 1S and 5S of the supplementary information give the equivalent
52
53 information to Figure 8 for the cases of ethylene glycol, glycerol, erythritol, adonitol and
54
55 sorbitol.
56
57
58
59
60 8
1
2
3
4
5
6
7
8
9
10
11
12
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15
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37
38
39
40
41
42
43
44
45
Figure 9. Change of the average heat of formation, E a , for each of the successive stages
46
47
48 of growth of the two branches of the PPO-2 polymer. The polymerization was initiated by
49
50 potassium ethyleneglycolate (two active sites). The pattern of the more energetically favored
51
52 polymer growth is shown at the top.
53
54
55
56
57
58
59
60 9
1
2
3
4
5
6
7
8
9
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11
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31
32
33
34
35
36
37
38
39
40
41
Figure 10. Change of average heat of formation, E a , for each of the successive stages of
42
43 PPO-3 branch growth. The reaction was initiated by potassium glycerolate (three active
44
45 sites). The pattern of the more energetically favored polymer growth is shown at the top.
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 10
1
2
3
4
5
6
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8
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33
34
35
36
37
38
39
40
41
42
43
44 Figure 11. Change of average heat of formation, E a , for each of the successive stages of
45
46 PPO-4 branch growth; the reaction was initiated by the potassium salt of erythritol (four
47
48 active sites). The pattern of the more energetically favored polymer growth is shown at the
49
50 top.
51
52
53
54
55
56
57
58
59
60 11
1
2
3
4
5
6
7
8
9
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22
23
24
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26
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28
29
30
31
32
33
34
35
36
37
38 Figure 12 Change of average heat of formation, E a , for each of the successive stages of
39
40 growth of PPO-4 branches; the reaction was initiated by the potassium salt of adonitol (five
41
42 active sites). The pattern of polymer growth more energetically favored is shown at the top.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 12
1
2
3
4
5
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7
8
9
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20
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22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37 Figure 13. Change of average heat of formation, E a , for each of the successive stages of
38
39
growth of PPO-3 branches; the reaction was initiated by potassium sorbitolate (six active
40
41
42 sites). The pattern of polymer growth more energetically favored is shown at the top.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 13
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 100
16 PO/EO-2
90
17
18
80
PO/EO-4
19
20 70
PO/EO-5
Water removal ( vol. %)
21
22 60
23
24 50 PO/EO-6
25
26 40
27 PO/EO-3
28 30 PO/EO-1
29
30 20
31
32 10 Blank
33
34 0
35
36 0 30 60 90 120 150 180 210 240 270 300
37 Time (min)
38
39
40
41 Figure 14. Water removal efficiency of multi-branched block copolymers in heavy crude oil
42
43 HCO1 (12.71 °API), dosed with 500 ppm of the dehydrating agents at 80 °C.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 14
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 100
16 90 PO/EO-1
17 PO/EO-3
18 80
19 PO/EO-5
Water removal (vol. %)
20 70
21 PO/EO-4
22 60
23 50
24
25
PO/EO-2
40
26
27 30
28
29 20
PO/EO-6
30 10 Blank
31
32 0
33
34 0 30 60 90 120 150 180 210 240 270 300 330
35
Time (min)
36
37
38
39 Figure 15. Water removal efficiency of multi-branched block copolymers in heavy crude oil
40
41 HCO1 (12.71 °API), dosed with 1000 ppm of the dehydrating agents at 80 °C.
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 15
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 100
16
17 90
18
19 80
20
21 70
PO/EO-2
22
23 60
24
25
50
26
27
40
28
29 PO/EO-6
30 30
31
32 20 PO/EO-5 PO/EO-1 PO/EO-3
33 PO/EO-4
34 10
35
36 0
37
38 0 30 60 90 120 150 180 210 240 270 300
39
40 Time (min)
41
42
43
44 Figure 16. Water removal as a function of time for an extra heavy crude oil HCO2 (9.68
45
46 °API), dosed with 500 ppm of the dehydrating agents at 80 °C.
47
48
49
50
51
52
53
54
55
56
57
58
59
60 16
1
2
3
4
5
6
7
8
9
10 100
11
12 90 PO/EO-2
13
14
PO/EO-6
80
15
16
70 PO/EO-5
17
18
19 60
20 PO/EO-4
21 50
22
23 40
24
25 30 PO/EO-1
26
27 20 PO/EO-3
28
29 10
30 Blank
31 0
32
33 0 30 60 90 120 150 180 210 240 270 300
34
35 Time (min)
36
37
38
39 Figure 17. Water removal as a function of time for an extra-heavy crude oil HCO2 (9.68
40
41 °API), dosed with 1000 ppm of the dehydrating agents at 80 °C.
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 17
1
2
3
4
5
6
7
8
9
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11
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13
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22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38 Figure 18. Image from the bottles used in the test with each multi-branched copolymers in
39
40 the HCO1 crude oil at a concentration of 1000 ppm, T = 80 °C and t = 300 min: (a) blank;
41
42 (b) PO/EO-1; (c) PO/EO-2; (d) PO/EO-3; (e) PO/EO-4; (f) PO/EO-5; and (g) PO/EO-6.
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 18
1
2
3
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6
7
8
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21
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25
26
27
28
29
30
31
32
33
34
35 Figure 19. Image from the bottles used in the test with each multi-branched copolymers in
36
37
HCO2 crude oil at a concentration of 1000 ppm, T = 80 °C and t = 300 min: (a) blank; (b)
38
39
40 PO/EO-1; (c) PO/EO-2; (d) PO/EO-3; (e) PO/EO-4; (f) PO/EO-5; and (g) PO/EO-6.
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60 19
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16 a) b) c)
17
18
19
20
21
22
23
24
25 Figure 20. Optical micrographs (resolution, 100 x) of the crude oil (HCO1, 12.71 ° API, H2O
26
27 = 39 vol%): a) crude oil without dehydrating treatment, b) the same crude oil after
28
29
dehydrating treatment ([PO/EO-5] = 1000 ppm, t = 300 min and 82 vol% of water removal),
30
31
32 c) crude oil after total dehydration ([PO/EO-5] = 1000 ppm, t = 720 min).
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
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60 20
1
2
3
4
5
6
7
8
9
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11
12
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24 Figure 21. Optical micrographs (resolution, 100 x) of the crude oil (HCO2, 9.68 ° API, H2O
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26 = 47 vol%): a) crude oil without any dehydrating treatment, b) the same crude oil after the
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28 dehydrating treatment ([PO/EO-5] = 1000 ppm, t = 300 min and 62 vol% of water removal),
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30 c) crude oil after total dehydration ([PO/EO-5] = 1000 ppm, t = 720 min).
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60 21

Synthesis, Characterization and Evaluation As Petroleum Demulsifiers of Multi-Branched Block Copolymers

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