SYNTHESES AND INVESTIGATION OF NONIONIC SURFACTANTS BASED ON VEGETABLE OIL FOR ENHANCED OIL RECOVERY

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1 THESES OF PhD DISSERTATION SYNTHESES AND INVESTIGATION OF NONIONIC SURFACTANTS BASED ON VEGETABLE OIL FOR ENHANCED OIL RECOVERY University of Pannonia Doctoral School of Chemical Engineering Sciences and Material Sciences Written by: ROLAND NAGY chemical engineer MSc research and development engineer MSc Supervisor: Dr. LÁSZLÓ BARTHA PROFESSOR EMERITUS UNIVERSITY OF PANNONIA FACULTY OF ENGINEERING INSITUTE OD CHEMICAL ENGINEERING AND PROCESS ENGINEERING DEPARTMENT OF MOL-HYDROCARBON AND COAL PROCESSING VESZPRÉM 2014

2 1. INTRODUCTION Parallel to the rapid development of the household chemicals and cosmetics industry, the research of surfactants has become more and more important in the past decades. Different surfactants were used as auxiliaries for chemical enhanced oil recovery in the petroleum industry. There are quite competitive to the conventional synthesis products of these industries, thus the results of this research are generally secret or could be only partially published. These conditions are related also to the research and development of the new test methods for the screening of the experimental products. The main screening methods, such as IFT measurement and the determination of some other physical or chemical characteristics are not enough, thus new qualification and selection methods are needed for the faster and more economic research. The assessment of the publications confirmed that the results gained by the previously used and new test methods are not independent from each other and only their combination can give real information about the usefulness of the surfactants. The individually assessed characteristics give only partial information about the effectiveness. The appropriate combination of physical, chemical, petroleum industrial and rheological testing methods should be used for the selection of the chemical EOR surfactants. It is probable that the successful selection of the surfactants could be possible only if the characteristics measured by all the important methods give satisfying value. Due to this statements it was necessary to develop a proprietary qualifying methodology to reduce the costs of surfactants for EOR practice. After the review of the publications it was supposed that a method must be evaluated for determination the characteristics of the surfactants and their mixtures. As the conditions of use are differ from the previous studies applied in the laboratory, further experiments were needed to be carry out where the circumstances approximate better the real parameters of the reservoir. The detection of the relationship between the various methods may be beneficial in the process of selection of surfactants.

3 Series of publications deal with the studies of interaction between the polymer and the surfactants, however the majority was based on the measurement of IFT. Valuable information about the additional studies is not available. It was necessary to expand the test methods for exploring the interaction and to develop a more detailed and accurate method to prove the interaction. The main task was to prepare and test the vegetable oil-based non-ionic surfactants using more environmentally friendly compounds during the synthesis. The goal was to investigate the possibilities for testing the composition of these non-ionic surfactants. The selection methods of the surfactants used individually and in mixtures intended to be developed. The appropriate composition (in particular the active substance content) is an important parameter in the further use of surfactants in chemical additive fields. 2. OBJECTIVES During my PhD research my first goal was to develop new efficient test methods and evaluation system for the screening of the experimental surfactants mixtures for the EOR technology. Another goal was to determine new knowledge how to influence data of the new selection methods. It can be explored the composition of the surfactant mixtures for properties of surfactants for EOR technology that based on the composition of surfactant can be optimized. 3. EXPERIMENTAL METHODS Conventional standard and non-standard analytical methods of analysis used for the structural identification and qualitative characterization the following:

4 A. Composition analysis of nonionic surfactants Gel permeation chromatography NMR spectroscopy HPLC-MS B. Determination of physical, chemical properties of nonionic surfactants Acid number Saponification number Solubility in water ROM value, HLB value C. Investigation of surfactants mixtures Oil flushing effect Emulsifying effect Emulsifying effect in reservoir condition Solubility in water Flooding test D. Stability tests if surfactants mixtures Mechanical stability Chemical stability Biological stability

5 3.1. Description of own developed methods The determination of composition of nonionic surfactant by gel permeation chromatography My aim was to study the possibilities of using the various modern methods and the equipment s of HPLC, GPC) before the experimental surfactants reliable analytical characterization. Furthermore, it was considered important to respond that previously or only limited published analytical methods suitable for this type of surfactants ever more accurate characterization. Determination of solubility in water The solubility is one of the main properties of the surfactants. Due to the nature of their solubility in water or oil is considered. The determination of this property for selection of the application area was also unnecessary. Indeed, if the surfactants mixtures are not sufficiently soluble in the water, then to the reservoir and injecting can be filtered and adsorbed the rock pores, which could reduce the oil recovery efficiency. Determination of HLB value An emulsion preparing with an emulsifier is depended partly on the HLB value. This feature also provides a measurement of the emulsifier best practical help to select a particular purpose. Based on previous experience, the measurement was necessary to develop a new solvent system and the development of a new, more accurate titration end point detection method.

6 Oil Flushing Effect The complex surface activity method has not been reported in the specific publications, which could be the extent to porous surfaces characterized by washing efficiency of the oil. It was developed a method for oil flushing effect, that based on the foundations of thin layer chromatography of organic chemical analysis has been used. Investigation of rheological properties On the basis literature data the examination of the viscosity of emulsions formed most commonly used rotational viscometer. Since settling quickly measure the viscosity of the emulsions by the conventional rotary rheometers proved inadequate, so on the department available Brookfield viscometer worked out a new test method. My goal was to create the future of oil-in-water emulsion a color inherently difficult to examine visually the characterization of a more reliable method of subjective visual alternative method is available. Determination of particle size and size distribution Characterization the polymer-surfactant solution rheology of the movable of fluid is also necessary. Previous results of the rheological measurements indicate that the dynamic viscosity of surfactant mixture in aqueous added to the flow modifier polymer is increased. The value of increase was greater than the effect of additive viscosity of polymer and a surfactant mixture. A significant number of literary publications mentioned only a change in the additive viscosity. It was assumed that it was produced a new colloidal system, that based on a new structure with the prosperous impact the test results of the positive interactions, synergies between the polymer and the surfactant molecules were confirmed.

7 4. NEW SCIENTIFIC RESULTS 1. The author has modified the conventional analytical method for the determination of the HLB (hydrophilic-lipophilic balance) value which is an important property of applied non-ionic surfactants used in surfactant mixtures. The previous titration method was completed with modern instrumental end point detection with the change of the carcinogenic benzene solvent with cyclohexane. a. It has proved that the HLB values determined with the developed method compared to the empirical HLB values were closely connected with the calculated HLB values according to the literature standards. It was presented by the correlation analysis where the deviation of the experimental HLB value from the calculated HLB value was less than 5%. 2. The author has developed a suitable method to determine the size and size distribution of colloid micelles in aqueous solutions that contained the flow modifier polymer and surfactants mixtures by light scattering. a. It was found that the size distribution of the efficient surfactants mixtures by crude oil flooding laboratory tests were located in the nm range. b. Interactions between the surfactants and flow modifier polymer were detected, which by a significant increase of particle sizes of the polymer-surfactant associates were confirmed. 3. It was realized that the polymer-surfactant associates of the surfactants mixtures and the flow modifier polymer have different structures. a. It was demonstrated that the surfactants mixtures that were created from the flow modifier polymer and variety of anionic and nonionic surfactants are different structure. It was proved by the concentration increases with the number of particles. Above the concentration of 10 g/dm 3 micelle structure was formed

8 (between 224 nm and 314 nm), and at more than 20 g/dm 3 concentration by further increased size of the micelles associates (between 486nm and 516 nm) were formed. This hypothesis was supported by the results of rheological measurements. b. It was observed that the solvated particle size of surfactant mixtures without the flow modifier polymer content have increased with increasing temperatures only less than a 5%, while the size of associates created from the surfactants mixtures and the flow modifier polymer increased about four-fold, that has been supported by the results of rheological measurements as well. 4. In the development of the test methods the approximate real conditions of reservoir conditions were introduced. These were the model measurements with Algyő stone fines and brine and the reservoir temperatures in the new test methods for the determination of oil flushing effect and the emulsifying effect as well. a. It was demonstrated that the results of the tests carried out by the previously model results significantly differ from that of results obtained by the real conditions approximating tests. b. It was found that some of the individual properties defined methods (IFT (Interfacial tension), EH (Emulsifying effect), TLC (Oil flushing effect)) with the results of the core flooding test could not be related. 5. A new evaluating system was created by using the results of three different test methods for selection of surfactants for chemical enhanced oil recovery. a. It was found that for the selection of chemical EOR surfactants one physicalchemical and two other special testing methods should be used together. It was proved that the successful selection of surfactants mixtures could be only possible if the selected compositions show a satisfactory efficiency obtained by all three methods in the case.

9 b. By the use of the developed methods the number of performed measurement can be approximately one-tenth reduced. c. A new equation was introduced which may be used for the selection of CEOR surfactants and by the estimation of the additional, available oil recovery based on a summarized rating number (CE) calculated from three measured properties of the experimented surfactants. (R 2 =0,805) where: CE, Complex Evaluate number, dimensionless VRK, Oil Flushing Effect, mm EH, Emulsifying effect, % IFT, Interfacial tension, mn/m

10 5. INDUSTRIAL APPLICATION OF THE RESULTS Laboratory test methods of the surfactants for EOR were developed which is the part of the preliminary selection of the combination of own-developed and the commercially available surfactants. The efficiency for EOR use can be estimated by this new, complex method in the first research phase. The number of measurements used in the selection of surfactants is reduced by this complex method which results a time-efficient and cost-effective research. The results of compositions of surfactants was selected by the pre-selection method have been found to be suitable for further use in large-scale experiments. In the future the selected surfactants will be produced by MOL-Lub Ltd. in a quantity of 1000 t.

11 6. LIST OF PUBLICATIONS Journal papers [1.] N. Miskolczi, R. Nagy: Hydrocarbons obtained by waste plastic pyrolysis: comparative analysis of decomposition described by different kinetic models, Fuel Processing Technology, 104, , 2012 [2.] Nagy R., Sallai R., Bartha L.: Tenzidek vízben való részleges oldhatóságának jellemzése száloptikás spektrofotométerrel, Anyagvizsgálók Lapja, 4., 2012, ISSN [3.] Nagy R., Bartha L., Tóth J., Vágó Á.: Study on characteristics of micelles formed by surfactants and polymer mixtures for enhanced oil recovery, Chemical Engineering Transactions, 36., 2014, ISSN [4.] Nagy R., Sallai R., Bartha L., Vágó Á.: Harmadlagos kőolajkitermelésre alkalmas tenzidek kiválasztási módszerei, EMMTT - Műszaki Szemle, 63., 2014, ISSN [5.] Nagy R., Sallai R., Bartha L., Vágó Á.: Study on solubility of surfactants in water by fiber optic spectrophotometer, Accepted for publication, The Journal Chemistry & Chemical Technology, 2014, ISSN [6.] Nagy R., Bartha L., Tóth J., Vágó Á., Dudás J.: Study on interaction of polymersurfactant mixtures used in chemical enhanced oil recovery, Submitted, Journal of Petroleum Exploration and Production Technology, 2015, ISSN [7.] Nagy R., Sallai R., Bartha L., Vágó Á.: Selection method of surfactants for chemical enhanced oil recovery, Submitted, Journal of Petroleum Science and Engineering, 2015, ISSN

12 Conference papers in hungarian [1.] Nagy R., Bartha L., Miskolczi N.: Víz növényolaj emulziók előállítására alkalmas tenzidek vizsgálata, XII. Nemzetközi Vegyészkonferencia, 2006, ISBN [2.] Nagy R., Miskolczi N., Bartha L.: Víz- növényolaj emulziók vizsgálata, Műszaki Kémiai Napok 07, 2007, [3.] Nagy R., Marton Zs., Bartha L.: Kőolajipari célokra előállított nemionos tenzidek összetételének kromatográfiás vizsgálatának lehetőségei, XV. Nemzetközi Vegyészkonferencia, Marosvásárhely, 2009, ISSN [4.] Nagy R., Marton Zs., Bartha L.: Nem-ionos tenzidek komplex kromatográfiás vizsgálata, Műszaki Kémiai Napok 10, Veszprém, 2010, ISBN [5.] Nagy R., Marton Zs., Bartha L.: Nemionos tenzidek spektrofotometriás vizsgálata, Vegyészkonferencia és 53. Magyar Spektrokémiai Vándorgyűlés, Hajdúszoboszló, ISBN [6.] Nagy R., Bartha L.:Nemionos tenzidek HLB számának meghatározása száloptikás spektrofotométerrel, XVI. Nemzetközi Vegyészkonferencia, Kolozsvár, 2010, ISSN [7.] Nagy R., Dr. Bartha L., Vágó Á.: Kőolajipari célú tenzidek nagynyomáson történő vizsgálata, XVII. Nemzetközi Vegyészkonferencia, Kolozsvár, 2011, ISSN [8.] Nagy R., Elekes A., Bartha L.:Kőolajipari célú tenzidkompozíciók emulgeáló hatásának vizsgálata nagy nyomáson, Műszaki Kémiai Napok 12, Veszprém, 2012, ISBN [9.] Molnár B., Nagy R., Bartha L.: Kőolaj-víz emulziók vizsgálatabrookfield rotációs viszkoziméterrel, Műszaki Kémiai Napok 12, Veszprém, ISBN

13 [10.] Sallai R., Nagy R., Bartha L.: Kőolajipari célokra előállított tenzidek oldhatóságának vizsgálata, Műszaki Kémiai Napok 12, Veszprém, ISBN [11.] Nagy R., Bartha L., Kiss Gy.: Nemionos tezidek folyadékkromatográfiás vizsgálata, Elválasztástudományi Vándorgyűlés, 2012 [12.] Sallai R., Nagy R., Bartha L.:Nemionos tenzidek kromatográfiás vizsgálata, XVIII. Nemzetközi Vegyészkonferencia, Nagyvárad, Románia, ISSN [13.] Nagy R., Sallai R., Bartha L.:EOR célú tenzidek vizes oldatának vizsgálata Malvern Zetasizerrel, XVIII. Nemzetközi Vegyészkonferencia, Nagyvárad, Románia, ISSN [14.] Sallai R., Nagy R., Bartha L.:Nemionos tenzidek gélkromatográfiás vizsgálata, Műszaki Kémiai Napok 13, Veszprém, ISBN [15.] Nagy R., Sallai R., Bartha L.: EOR célú tenzidkompozíciók vizes oldatának részecskeméret vizsgálata Malvern Zetasizerrel, Műszaki Kémiai Napok 13, Veszprém, ISBN [16.] Nagy R., Sallai R., Bartha L.:Kőolaj-víz emulziók reológiai vizsgálata, Műszaki Kémiai Napok 13, Veszprém, ISBN [17.] Sallai R., Elekes A., Nagy R., Bartha L.: Kőolaj-víz emulziók reológiai vizsgálata Brookfield rotációs viszkoziméterrel, Környezetbarát anyagok és technológiák" Konferencia és 56. Magyar Spektrokémiai Vándorgyűlés, július 1-3., Veszprém, [18.] Nagy R.,Sallai R., Bartha L.: Tenzidek vizsgálati módszerei kémiai EOR vélra (EOR technológiákban alkalmazható tenzidek hatásvizsgálati módszereinek továbbfejlesztése), Környezetbarát anyagok és technológiák" Konferencia és 56. Magyar Spektrokémiai Vándorgyűlés, július 1-3., Veszprém [19.] Nagy R., Sallai R., Bartha L., Vágó Á.: Tenzidkompozíciók vizsgálati módszerei kémiai EOR célra, XIX. Nemzetközi Vegyészkonferencia, november , Nagybánya, ISSN

14 [20.] Nagy R., Sallai R., Bartha L., Vágó Á.: Harmadlagos kőolaj kitermelésre felhasználandó tenzidek laboratóriumi szelekciójának hatásvizsgálati módszerei,mta Kémiai Technológia Munkabizottság, december 13., BME, Budapest [24.] Nagy R., Sallai R., Bartha L., Vágó Á.: Kőolajipari célokra előállított tenzidek HLB értékének vizsgálata, XIX. Fiatal Műszakiak Tudományos Ülésszaka, 2014.március , Kolozsvár, ISSN [25.] Nagy R., Elekes A., Sallai R., Bartha L., Vágó Á.: Kémiai harmadlagos kőolajkitermelés során előállítható kőolaj-víz emulziók reológiai vizsgálata, Műszaki Kémiai Napok 14, május , Veszprém, ISBN [26.] Nagy R., Kothencz R., Sallai R., Bartha L., Tóth J., Vágó Á.: EOR célra előállított tenzidek vizes oldatainak részecskeméret vizsgálata, Műszaki Kémiai Napok 14, május , Veszprém, ISBN [27.] Nagy R., Sallai R., Bartha L., Tóth J., Vágó Á.: Kémiai harmadlagos kőolajkitermelésre felhasználható polimer és tenzidek oldata viszkozitás-hőmérséklet karakterisztikájának vizsgálata, Pannon Tudományos Nap, Nagykanizsa, [28.] Elekes A., Nagy R., Bartha L., Vágó Á.: Kémiai harmadlagos kőolaj-kitermelés során előállítható kőolaj-víz emulziók reológiai vizsgálata Brookfield rotációs viszkoziméterrel, XX. Nemzetközi Vegyészkonferencia, Kolozsvár,2014,ISSN [29.] Kothencz R., Nagy R., Bartha L., Vágó Á.: CEOR célú polimeres tenzid oldatok reológiai vizsgálata, XX. Nemzetközi Vegyészkonferencia, 2014, Kolozsvár, ISSN [30.] Nagy R., Kothencz R., Bartha L., Vágó Á.: Kémiai harmadlagos kőolajkitermelés során termelt kőolaj vizsgálata, XX. Nemzetközi Vegyészkonferencia, 2014, Kolozsvár, ISSN

15 Conference papers in english [1.] R. Nagy, L. Bartha, Á. Vágó: Investigation of non-ionic surfactants for Enhanced Oil Recovery, Interfaces 11, Sopron [2.] R. Nagy, L. Bartha, J.Tóth, J.Dudás, Á. Vágó: Study on characteristics of micelles formed by surfactants and polymer mixtures for enhanced oil recovery, 10th Conference on Colloid Chemistry, Budapest, ISBN [3.] Nagy R., Bartha L., Tóth J., Vágó Á.: Investigation of size of surfactants for EOR by Malvern Zetasizer, Challenges and future technologies for the implementation of EOR, Szolnok [4.] R.Nagy, R.Sallai, L. Bartha, Á. Vágó: Investigation of solubility of surfactants in water by fiber optic spectrophotometer, 41 st International Conference of SSCHE, May 2014., Tatranské Maliare, Slovakia, ISBN