Green-Inspired Synthesis and Industrial Applications of Branched

Letter pubs.acs.org/journal/ascecg

Green-Inspired Synthesis and Industrial Applications of Branched Geminal Zwitterionic Liquids Jorge Francisco Ramírez-Pérez,† Ricardo Cerón-Camacho,*,‡ Enrique Soto-Castruita,‡ Violeta Yazmín Mena-Cervantes,§ Raúl Hernández-Altamirano,§ Rodolfo Cisneros-Dévora,‡ José Manuel Martínez-Magadán,† and Luis Silvestre Zamudio-Rivera*,† †

Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, Col. San Bartolo Atepehuacán, CDMX 07730, México CONACyT-Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, Col. San Bartolo Atepehuacán, CDMX 07730, México § Centro Mexicano para la Producción más Limpia, Instituto Politécnico Nacional, Avenida Acueducto s/n, Col. La Laguna Ticomán, CDMX 07340, México ‡

S Supporting Information *

ABSTRACT: We prepared geminal zwitterionic liquids with the capability to obtain the chemical active species from laboratory to scalable production with pure or raw materials. Hence, a green-inspired and efficient process for their synthesis was developed. A performance test at reservoir conditions was conducted and it was found that the synthesized chemicals increase the oil recovery factor in an enhanced oil recovery process with properties as antiscale agents.

KEYWORDS: Branched geminal zwitterionic liquids, Green chemistry, Green synthesis, Nontoxic products, Enhanced oil recovery application

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INTRODUCTION Ionic liquids exhibit relevant and significant properties for several industrial applications including high stability over a wide range of temperatures, no volatility, no flammability, high electrical conductivity and large ion diffusion coefficients.1,2 Recently, some researchers have designed new ionic liquids where both anion and cation coexist in the same molecule with a total zero net charge, the so-called zwitterionic compounds, in accordance with IUPAC, for example the amino acids molecules.3 Their applications are wide in fields such as conductive matrices, electrochemistry or lithium batteries.1,2,4 In other applications, some zwitterionic liquids are used as surfactants in enhanced oil recovery (EOR) processes. In this context, one of the technological EOR options is the use of zwitterionic liquids because they have the ability to reduce the interfacial tension of the oil−water phase and to modify rock wettability from oil-wet to water-wet.5−7 In this operation field, zwitterionic liquids represent an advantage with respect to other chemicals because they are compounds electrically neutral containing both positive and negative electrical charges through different functional groups in the same molecule, which gives the opportunity to behave as Lewis acids or bases, i.e., electron acceptor or donor, depending the properties of the medium. In other words, molecules capable of adapting to © 2017 American Chemical Society

different media and therefore can be designed in such a way that responds effectively to the operating conditions.8 In accordance with Anastas and Warner, green chemistry is the utilization of a 12 principles to reduce or eliminate the use or generation of hazardous substances in the design, manufacture and application of chemical products.9 The chemical industry requires chemicals with multifunctional characteristics within an environmental scope. In this effort, we have synthesized zwitterionic liquids through a greeninspired process such that each reagent will be part of the molecular structure in the final product, where byproducts formation does not represent any type of environmental contamination.7,10 We have obtained efficiently and cleanly a branched geminal zwitterionic liquids in a reaction vessel in only two steps.11 The reported synthesis differs from that of similar surfactants containing zwitterionic liquids, which involves toxic agents, solvents and additional purification steps.5−7 We have found a new greener method of synthesis with a high atom economy, reaction mass efficiency (RME) and corresponding E-factor in Received: June 2, 2017 Revised: July 7, 2017 Published: July 14, 2017 6404

DOI: 10.1021/acssuschemeng.7b01760 ACS Sustainable Chem. Eng. 2017, 5, 6404−6408

Letter

ACS Sustainable Chemistry & Engineering Scheme 1. General Synthetic Route for Prepare Green-Inspired Branched Geminal Zwitterionic Liquids

to obtain branched geminal zwitterionic liquids in a one pot reaction only in two steps. In the first step occurs the reaction between PEGDGE and a secondary amine in a 1:2 stoichiometric ratio, without solvent at 100−120 °C, and stirring for 6 h. The geminal branched nonzwitterionic liquid is obtained, as a consequence of the nucleophilic attack to epoxy group, giving the aperture of the ring to form a new C−N bond and the corresponding hydroxyl group. Here, the product is a viscous liquid. The second step occurs in the same flask for the zwitterion formation, through the reaction of the geminal branched nonzwitterionic precursor produced in the previous step, with sodium chloroacetate in a 1:2 mol ratio, using water in the reaction medium and under reflux conditions for 8−12 h. Finally, the zwitterionic liquid and an aqueous phase that contains sodium chloride is produced (Scheme 1). This brine was removed by decantation to obtain the corresponding branched geminal zwitterionic compound with yields up to 94% (Table 1).

accordance with a reaction process friendly to the environment. The spontaneous imbibition tests showed the green-inspired zwitterionic compounds suitability in oil production.

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EXPERIMENTAL SECTION

Poly(ethylene glycol)diglycidyl ether (PEGDGE) with average molecular weight of Mn 500 and Mn 1000, sodium chloroacetate and dioctyl amine were obtained from Aldrich Chemical Co. Industrial dicocoalkylamine with average length chain C12−14 was provided by AzcoNovel and used as received. All NMR spectra, 1H and 13C, were performed on a Bruker Advance III 300 spectrometer in CDCl3. Chemical shifts (δ) are in ppm and referenced to the TMS peak. Coupling constants (J) are in Hz. IR spectra were recorded on an IR Smith HAzMathID 360 using ATR mode. Microscope images were made in a Philips XL30 FEG scanning electron microscope. The oil recovery factor (ORF) is obtained in Amott Cells, which consists of a temperature-controlled container with a graduated capillary tube located at the top, where the extracted oil is collected. The rock cores are embedded in oil as per the previously published procedure.12 General Procedure To Prepare Geminal Branched Zwitterionic Liquids. Step 1. In a flask is poured PEGDGE as a viscous liquid (0.018 mol) and secondary amine (0.036 mol). Under atmospheric conditions, the mixture is stirred and heated to 120 °C for 6 h. After that time, a change in the color to a slightly yellow is observed. Just a small sample was taken for spectroscopic characterization. Step 2. In the same flask are added the stoichiometric amount of sodium chloroacetate (0.036 mol) and 5 g of water as auxiliary solvent. The mixture is stirred and heated under reflux conditions by 8−12 h. Later, the reaction mixture is cooled to room temperature and the aqueous phase removed by decantation. An orange to red viscous liquid, the geminal branched zwitterionic compound is recovered. Spectroscopy data for all compounds are available in the Supporting Information.

Table 1. Green Metric Values Comparing All Chemical Prepared in This Worka Product

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a

RESULTS AND DISCUSSION As compared to other similar zwitterionic liquids prepared by our research group,12 this new synthetic route, as presented here, is greener and with novelty value. Specifically, the older methodology is multistep, uses arylsulfonyl choride derivatives, basic reagents in excess, solvents such as choloroform, NCMe or THF, and involves complicated purification steps such as extraction, filtrations and evaporations, among others. In the current case, we have found a new simple, easy and clean route

Yield

1 2 3 4

1 1 1 1

1a 2a 3a 4a

0.995 0.990 0.989 0.944

Atom Economy

Reaction Mass Efficiency

Branched geminal precursors 1 1 1 1 1 1 1 1 Branched geminal zwitterionic liquids 0.907 0.903 0.924 0.915 0.925 0.915 0.943 0.937

Efactor 0.002 0.002 0.001 0 0.218 0.176 0.175 0.129

The values are expressed in absolute form between 0 and 1.

The yields are very good in the two synthetic steps. This synthetic procedure is used for not only ACS grade secondary amines but also for industrial grade amines with the aim to evaluate the possibility to obtain the chemicals in an industrial scale. In our experience, this is potentially possible.11 In compliance with IUPAC rules in naming of zwitterionic chemicals,13 we name our product as 2,2′-((poly(ethylene 6405


Letter

ACS Sustainable Chemistry & Engineering

Figure 1. 13C NMR spectra (left) and zoom 1H NMR (right) spectra for PEGDGE; their respective intermediate 1 and the corresponding zwitterionic product 1a corresponding signal for CO appears at 178.8 ppm.

system for natural-waters and waste-waters.19 Consistent with this, toxicity categories the zwitterionic liquids are better, i.e., less toxic than other surfactants as alkyl ethoxysulfate or the quaternary ammonium ionic liquids, as reported in specialized literature.20−22 This is the principal evidence that allows us to consider this synthesis for its implementation at industrial scale, for having environment friendly characteristics and low toxic levels. Additionally, we are able to monitor the reaction by IR spectroscopy, which is available at the industrial level and it is cheaper, easier and faster than NMR spectroscopy but with the same effectivity. In Figure 2, the IR-ATR spectra for a PEGDGE, the respective intermediate 1 and the corresponding final product 1a are shown. For a better evaluation, we selected compound 1a for corresponding monitoring by IR spectroscopy. Initially, the PEGDGE (Figure 2) spectrum basically shows the band of the CH bonds from ethylene groups, the C−O bonds for the ether

oxide)bis(2-hydroxypropane-3,1-diyl))bis(dialkylammoniumdiyl))diacetate. In Table 1, we observe the calculated green metric values: the atom economy (AE) defined as all atoms of reactants found in the desired product,14 the reaction mass efficiency (RME) provides information about the ratio between mass for main product and the total mass input,15 and the environmental factor Efactor is the amount of waste produced in the chemical process.16 1 H and 13C NMR indicate the first step is nearly quantitative in yield (see Scheme 1 and Figure 1), where consumption of all the reactants to form the desired precursor 1 was confirmed by the disappearing of signals corresponding to epoxy ring from PEGDGE. The respective zooms of 1H NMR spectra for the intermediate 1 and PEGDGE are shown in Figure 1. Here, the MRE and AE values are estimated to be 1 based on the observed data; in other words, all atoms are incorporated in the product. Accordingly the Efactor values are near zero. In the second step, which corresponds to the zwitterionic liquid formation 1a (Figure 1) where the yield is up to 94%, the AE and MRE data are around 0.9. This is attributed to the formation of NaCl. However, the Efactor records are very low, between 0.1 and 0.2. In a general process, for all desired zwitterionic liquids, their yield, AE, MRE and Efactor values are in accordance with the desirable values for a green process. We noticed the reaction in the first step is not affected by neither the length of the polymer chain of PEGDGE nor the purity of the secondary amine because the yields and AE are good when we use amine ACS grade or an industrial mixture. Acute toxicity tests with Artemia franciscana were performed for zwitterionic liquids obtained from industrial raw materials according to the standard method.17 We observe their LC50 values are between 97 and 172 mg/L, which indicates these chemicals are practically nontoxic according to North Sea toxicity categories (range LC/EC50 for toxicity test in mg/L: 100−1000 practically nontoxic; >1000 nontoxic)18 for use of chemicals in the offshore oil industry and the classification

Figure 2. IR spectra for PEGDGE, their respective intermediate 1 and the corresponding final product 1a. The main bands are CN and CO. 6406


Letter


Figure 3. SEM micrographs of (a) pure NaCl without zwitterionic liquid, (b) branched geminal zwitterionic liquid 1a with NaCl traces and (c) pure branched geminal zwitterionic liquid 1a.

linkages in 2867, 1451 and 1100 cm−1, respectively. When the reaction with dioctylamine occurs, new bands appear at 3456 cm−1 that correspond to the −OH group and at 1464 cm−1 to a new C−N bond due to aperture of the epoxy ring that corresponds to intermediate 1 (Figure 2). The final zwitterionic liquid, product 1a, is formed by the quarternization of amino group with the addition of an acetate group; this can be monitored by the corresponding carbonyl group at 1625 cm−1 (Figure 2). In Figure 3, the scanning electron microscopy (SEM) pattern of the zwitterionic liquid 1a, at 2000 ppm, forms a homogeneous layer as shown specifically in Figure 3C. Pure NaCl has a distinct crystalline shape. Trace NaCl in 1a shows a significantly different pattern that is characteristic of inhibition of NaCl crystallization. We interpret these results as evidence that 1a can inhibit scaling of inorganic salts.23 Spontaneous imbibition tests for compounds were performed, according to the molecular weight, 1a and 3a, for pure reagents and 2a and 4a, for compounds obtained from raw materials. Then, a comparison with the behavior of the system without the presence of any additives was done. For this purpose, calcite cores of 38 mm diameter and 69 mm length with a permeability around 200 mD were immersed in heavy crude oil with an API of 12 for 24 h at 90 °C. The total oil embedded was determined by weight difference. Under these conditions, the branched geminal zwitterionic liquids are thermally stable. Corresponding TGA thermograms show stability to 120 °C, and after this at 200 °C the total decomposition occurs (see Supporting Information). After that process, the rock cores were placed in an Amott Cell with seawater with or without the zwitterionic compounds. The oil production was determined after 11 days at 90 °C. In Figure 4, a comparison in the contact angle of the oil over rock core in the presence of seawater and the compound 1a is presented. It can be seen that, even after 11 days, the core in pure seawater is covered by the oil, with a contact angle of 16°, which means the rock has an affinity for the oil, i.e., the rock is

oil-wet. Though the surface of the rock core in the presence of the 1a has scarce oil, with a contact angle of 157°, i.e., the rock is water-wet. Furthermore, in the presence of the chemical product, the remaining oil produces drops, which is clear evidence of the change in the rock wettability as shown in Figure 4. This is according to the principal molecular mechanism related to the increase in oil production when the new chemical product is present.12 Therefore, the rock is wet by the water instead of the oil. Table 2 shows the oil recovery factor of the mentioned systems. The seawater is able to recover less oil from the core in Table 2. Oil Recovery Factor for Calcite Cores in Seawater without or with the Presence of Zwitterionic Liquids for 11 days at 90°C Amott cell Seawater 1a, 2000 ppm 3a, 2000 ppm 2a, 2000 ppm 4a, 2000 ppm

Oil recovery factor, %

Ratio recovered oil and recovered oil in seawater

1.25 4.24

1 3.4

10.24

8.2

11.7

9.4

9.27

7.4

comparison with the oil recovered with the zwitterionic compounds diluted in seawater, which increase the oil recovery factor in more than 3 times, a fact that is an excellent result for this kind of chemicals.

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CONCLUSIONS We have discussed a green and clean chemical synthesis of branched geminal zwitterionic liquids where calculated metrics show our process is friendly to the environment, and the method is suitable to set up at the pilot or industrial level. The geminal zwitterionic liquids’ capability to change the rock wettability and consequently increase of the oil recovery factor make these chemicals an ideal option to be applicable in enhanced oil recovery processes and in other potential applications such as antiscale agents of inorganic salts.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b01760. Spectroscopy data for all compounds, detail of Ammot cells and oil recovery factors (PDF)

Figure 4. Calcite cores embedded in heavy oil for 11 days at 90 °C in the presence of seawater (left) and 2000 ppm of 1a in seawater (right). 6407


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́ Oviedo Roa, R.; Cartas Rosado, A. R.; Ramírez Estrada, A. Liquidos Zwitteriónicos Geminales Ramificados, Proceso de Obtención y Uso Como Modificadores de la Mojabilidad con Propiedades Reductoras de la Viscosidad. Patent WO2015178753, November 26, 2015. (11) Mena Cervantes, V. Y.; Hernández Altamirano, R.; Zamudio Rivera, L. S.; Ramírez Estrada, A.; Ramírez, P. J. F.; Martínez Magadan, J. M.; Cisneros Devora, R. Hydroxypropyl Betaine Based Zwitterionic Geminal Liquids, Obtaining Process and Use as Wettability Modifiers with Inhibitory/Dispersants Properties of Asphaltenes. Patent US20160168447A1, June 16, 2016. (12) Ramírez-Pérez, J. F.; Hernández-Altamirano, R.; MartínezMagadán, J. M.; Cartas-Rosado, R.; Soto-Castruita, E.; CisnerosDévora, R.; Alcázar-Vara, L. A.; Oviedo-Roa, R.; Mena-Cervantes, V. Y.; Zamudio-Rivera, L. S. Synthesis of branched geminal zwitterionic liquids as wettability modifiers in enhanced oil recovery processes. J. Ind. Eng. Chem. 2017, 45, 44−55. (13) Favre, H. A.; Powell, W. H. Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013; Royal Society of Chemistry: Cambridge, 2013. DOI: 10.1039/9781849733069. (14) Trost, B. The atom economy-a search for synthetic efficiency. Science (Washington, DC, U. S.) 1991, 254 (5037), 1471−1477. (15) Andraos, J. Unification of Reaction Metrics for Green Chemistry: Applications to Reaction Analysis. Org. Process Res. Dev. 2005, 9 (2), 149−163. (16) Dicks, A. P.; Hent, A. Green chemistry metrics: a guide to determining and evaluating process greenness; Springer International Publishing: London, 2015. DOI: 10.1007/978-3-319-10500-0. (17) Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, 5th ed; EPA-821-R-02012; US EPA: Washington, DC, 2002. (18) Whale, G. F.; Whitham, T. S. Methods for Assessing Pipeline Corrosion Prevention Chemicals on the Basis of Antimicrobial Performance and Acute Toxicity to Marine Organisms. In SPE Health, Safety and Environment in Oil and Gas Exploration and Production Conference; Society of Petroleum Engineers, 1991. DOI: 10.2118/ 23357-MS. (19) Persoone, G.; Marsalek, B.; Blinova, I.; Törökne, A.; Zarina, D.; Manusadzianas, L.; Nalecz-Jawecki, G.; Tofan, L.; Stepanova, N.; Tothova, L.; et al. A practical and user-friendly toxicity classification system with microbiotests for natural waters and wastewaters. Environ. Toxicol. 2003, 18 (6), 395−402. (20) Sibila, M. A.; Garrido, M. C.; Perales, J. A.; Quiroga, J. M. Ecotoxicity and biodegradability of an alkyl ethoxysulphate surfactant in coastal waters. Sci. Total Environ. 2008, 394 (2), 265−274. (21) Zackiewicz, J.; Jakubowska, A. Toxicity of quaternary ammonium ionic liquids to aquatic organisms. CHEMIK 2015, 69 (8), 477−484. (22) Hernández-Altamirano, R.; Mena-Cervantes, V. Y.; PerezMiranda, S.; Fernández, F. J.; Flores-Sandoval, C. A.; Barba, V.; Beltrán, H. I.; Zamudio-Rivera, L. S. Molecular design and QSAR study of low acute toxicity biocides with 4,4¢-dimorpholyl-methane core obtained by microwave-assisted synthesis. Green Chem. 2010, 12, 1036−1048. (23) Pons-Jiménez, M.; Hernández-Altamirano, R.; Cisneros-Dévora, R.; Buenrostro-González, E.; Oviedo-Roa, R.; Martínez-Magadán, J.M.; Zamudio-Rivera, L. S. Theoretical and experimental insights into the control of calcium sulfate scales by using random copolymers based on itaconic acid. Fuel 2015, 149, 66−77.

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (R. Cerón-Camacho). *E-mail: [email protected] (L. S. Zamudio-Rivera). ORCID

Ricardo Cerón-Camacho: 0000-0003-2757-4963 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors are grateful to the Mexican Institute of Petroleum (IMP) for providing facilities and grant permission to publish the results. This work was supported by the IMP project ́ D.61029. J. F. Ramirez-Pé rez acknowledges the financial support from CONACyT and IMP for a Ph.D. scholarship grant. R. Cerón-Camacho, E. Soto-Castruita and R. CisnerosDévora thank Dirección de Cátedras CONACyT for its appointments.

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ABBREVIATIONS PEGDGE, poly(ethylene glycol)diglycidyl ether; AE, atom economy; RME, reaction mass efficiency; Efactor, environmental factor; NMR, nuclear magnetic resonance; IR, infrared spectra; SEM, scanning electron microscopy; ORF, oil recovery factor; EOR, enhanced oil recovery

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REFERENCES

(1) Yoshizawa-Fujita, M.; Narita, A.; Ohno, H. Zwitterionic Liquids. In Electrochemical Aspects of Ionic Liquids; John Wiley & Sons, Inc.: Hoboken, NJ, 2011; pp 301−316. DOI: 10.1002/ 9781118003350.ch21. (2) Ohno, H. Functional Design of Ionic Liquids. Bull. Chem. Soc. Jpn. 2006, 79 (11), 1665−1680. (3) Zwitterionic compounds/zwitterions. IUPAC Compendium of Chemical Terminology; International Union of Pure and Applied Chemistry: Zürich, 1997. (4) Ohno, H.; Fukumoto, K. Amino Acid Ionic Liquids. Acc. Chem. Res. 2007, 40 (11), 1122−1129. (5) Lopez-Chavez, E.; Garcia-Quiroz, A.; Gonzalez-Garcia, G.; Orozco-Duran, G. E.; Zamudio-Rivera, L. S.; Martinez-Magadan, J. M.; Buenrostro-Gonzalez, E.; Hernandez-Altamirano, R. Quantum chemical characterization of zwitterionic structures: Supramolecular complexes for modifying the wettability of oil−water−limestone system. J. Mol. Graphics Modell. 2014, 51, 128−136. (6) Cisneros-Dévora, R.; Nieto-Á lvarez, D. A.; Cerón-Camacho, R.; Pérez-Á lvarez, M.; Cartas-Rosado, A. R.; Oviedo-Roa, R.; MartínezMagadán, J. M.; Zamudio-Rivera, L. S.; Pons-Jiménez, M.; HernándezAltamirano, R.; et al. Molecular modeling, synthesis and characterization of branched geminal zwitterionic liquids for enhanced oil recovery. Arabian J. Chem. 2016, DOI: 10.1016/j.arabjc.2016.05.011. (7) Alcázar-Vara, L. A.; Zamudio-Rivera, L. S.; Buenrostro-González, E.; Hernández-Altamirano, R.; Mena-Cervantes, V. Y.; Ramírez-Pérez, J. F. Multifunctional Properties of Zwitterionic Liquids. Application in Enhanced Oil Recovery and Asphaltene Aggregation Phenomena. Ind. Eng. Chem. Res. 2015, 54 (11), 2868−2878. (8) Hernández Altamirano, R.; Zamudio Rivera, L. S.; Mena Cervantes, V. Y.; Beltrán, C. H. I.; Durán, V. C. D. L. Á .; López Ramírez, S.; Buenrostro González, E.; Mendoza De, L. C. J. L.; García, M. J. A.; Luna Rojero, E. E.; et al. Composition Based on Geminals Zwitterionics Liquids As Wettability Modifiers in Enhanced Oil Recovery Processes. Patent US20130296200A1, November 7, 2013. (9) Anastas, P. T.; Warner, J. C. Green chemistry: Theory and practice; Oxford University Press: Oxford, 1998. (10) Ramírez Pérez, J. F.; Hernández Altamirano, R.; Mena Cervantes, V. Y.; Zamudio Rivera, L. S.; Cisneros Dévora, R.; 6408


Green-Inspired Synthesis and Industrial Applications of Branched

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