Optimization of Tall Oil Pitch Saponification by Experimental Design
DOI:
https://doi.org/10.37482/0536-1036-2022-1-173-187Keywords:
tall oil pitch, phytosterols, saponification, process optimization, central composite design, response surface methodologyAbstract
Sustainable recycling of wood chemical production wastes is one of the current issues of modern technology. As a by-product of the pulp and paper industry, tall oil pitch has found application as a potential source of phytosterols. Phytosterols or plant sterols are natural compounds, polycyclic alcohols structurally similar to steroids. Due to their biological activity, phytosterols are used in such areas as pharmaceutics and cosmetology, as functional products, etc., which makes them commercially attractive. This paper considers the stage of saponification of tall oil pitch, which yields free phytosterols from their esters with fatty and resin acids. A central composite design complemented by six star points was chosen to determine the combined effect of the three factors and to plan the minimum number of experiments; the response surface methodology was used to determine the optimal values of the variables. Regression models showing the impact of the basic technological factors (excess alkali, temperature and duration of saponification) on the degree of saponification of phytosterols in saponified tall oil pitch and esters in the obtained extract were developed based on the experimental data. A statistical analysis of the models was carried out. Their validity has been proved by means of analysis of variance. The experimental and predicted values closely correlated. The developed mathematical models in the regression polynomial form enable to find the optimal values of the input process variables using the Minitab software while
simultaneously reaching the maximum degree of saponification (98,1 %) with the minimum value of the ether number in the extract (4 mg KOH/g): saponification temperature – 121.7 °C, process duration – 3.18 h, and excess alkali – 100 %. Thus, reliable models for predicting the degree of saponification of phytosterols and the ester number in the extract were obtained. These models can be used in industrial saponification of tall oil pitch.
For citation: Korshunov A.O., Lavrenteva E.A., Lazarev M.A., Radbil’ A.B. Optimization of Tall Oil Pitch Saponification by Experimental Design. Lesnoy Zhurnal [Russian Forestry Journal], 2022, no. 1, pp. 173–187. DOI: 10.37482/0536-1036-2022-1-173-187
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Богомолов Б.Д., Сапотинцкий С.А., Соколов О.М. и др. Переработка сульфатного и сульфитного щелоков / под. ред. Б.Д. Богомолова, С.А. Сапотницкого. М.: Лесн. пром-сть, 1989. 360 с. Bogomolov B.D., Sapotintskiy S.A., Sokolov O.M. et al. Processing of Sulphate and Sulphite Liquors. Ed. by B.D. Bogomolov, S.A. Sapotnitskiy. Moscow, Lesnaya promyshlennost’ Publ., 1989. 360 p.
Веденяпина М.Д., Стопп П., Вайхгребе Д., Веденяпин А.А. Применение метода поверхности отклика для изучения адсорбции диклофенака натрия из водных растворов на активированном угле // Химия твердого топлива. 2016. № 4. С. 61–63. Vedenyapina M.D., Vedenyapin A.A., Stopp P., Weichgrebe D. Application of a Response Surface Method to Studying the Adsorption of Diclofenac Sodium from Aqueous Solutions on Activated Carbon. Khimiya tverdogo topliva [Solid Fuel Chemistry], 2016, no. 4, pp. 61–63. DOI: https://doi.org/10.7868/S0023117716040113
Гордон Л.В., Скворцов С.О., Лисов В.И. Технология и оборудование лесохимических производств. 5-е изд., перераб. М.: Лесн. пром-сть, 1988. 360 с. Gordon L.V., Skvortsov S.O., Lisov V.I. Technology and Equipment for Chemical Production. Moscow, Lesnaya promyshlennost’ Publ., 1988. 360 p.
ГОСТ 17823.1–72. Продукты лесохимические. Метод определения кислотного числа: дата введения 1973–07–01. М.: Изд-во стандартов, 1999. 4 с. State Standard. GOST 17823.1–72. Wood Chemical Products. Method of Acid Number Determination. Moscow, Izdatel’stvo standartov, 1999. 4 p.
ГОСТ 5478–2014. Масла растительные и натуральные жирные кислоты. Метод определения числа омыления: дата введения 2016–01–01. М.: Стандартинформ, 2015. 8 с. State Standard. GOST 5478–2014. Vegetable Oils and Natural Fatty Acids. Method for Determination of Saponification Value. Moscow, Standartinform Publ., 2015. 8 p.
Дымент О.Н., Казанский К.С., Мирошников А.М. Гликоли и другие производные окисей этилена и пропилена. М.: Химия, 1976. 376 с. Dyment O.N., Kazanskiy K.S., Miroshnikov A.M. Glycols and Other Derivatives of Ethylene and Propylene Oxides. Moscow, Khimiya Publ., 1976. 376 p.
Исмагилов Р.М. Технология получения новых продуктов на основе таллового пека: дис. … канд. техн. наук. Нейво-Рудянка, 2004. 125 с. Ismagilov R.M. Technology for Obtaining New Products Based on Tall Oil Pitch: Cand. Eng. Sci. Diss. Neyvo-Rudyanka, 2004. 125 p.
Исмагилов Р.М., Радбиль А.Б., Радбиль Б.А. Пути квалифицированного использования таллового пека // Химия растит. сырья. 2004. № 2. C. 73–76. Ismagilov R.M., Radbil’ A.B., Radbil’ B.A. Ways of Qualified Use of Tall Oil Pitch. Khimija rastitel’nogo syr’ja [Chemistry of plant raw material], 2004, no. 2, pp. 73–76.
Клюев А.Ю., Скаковский Е.Д., Козлов Н.Г., Прокопчук Н.Р., Латышевич И.А. Получение и антисептические свойства состава на основе таллового пека // Изв. Нац. акад. наук Беларуси. Сер. хим. наук. 2016. № 1. С. 82–87. Kliuyeu A.Yu., Skakovskiy E.D., Kozlov N.G., Prokopchuk N.R., Latyshevich I.A. Preparation and Antiseptic Properties of the Composition Based on Tall Pitch. Vescì Nacyânalʹnaj akadèmìì navuk Belarusì. Seryâ hìmìčnyh navuk [Proceedings of the National Academy of Sciences of Belarus, Chemical Series], 2016, no. 1, pp. 82–87.
Некрасова В.Б., Безбородова Т.Г. Получение и применение биокорректоров питания из биомассы дерева // Изв. СП бЛТА . 2012. № 198. С. 190–201. Nekrasova V.B., Bezborodova T.G. Preparation and Application of Biocorrector Supply from Wood Biomass. Izvestia Sankt-Peterburgskoj Lesotehniceskoj Akademii [News of the Saint Petersburg State Forest Technical Academy], 2012, no. 198, pp. 190–201.
Некрасова В.Б., Евстигнеев Э.И. Определение оптимальных параметров процесса омыления таллового пека // Изв. вузов. Лесн. журн. 1976. № 4. С. 113–116. Nekrasova V.B., Evstigneyev E.I. Determination of Optimal Parameters of Tall Oil Pitch Saponification. Lesnoy Zhurnal [Russian Forestry Journal], 1976, no. 4, pp. 113–116. URL: http://lesnoizhurnal.ru/apxiv/1976/1976-%E2%84%964.pdf
Овчинников Ю.А. Биоорганическая химия. М.: Просвещение, 1987. 815 с. Ovchinnikov Yu.A. Bioorganic Chemistry. Moscow. Prosveshcheniye Publ., 1987. 815 p.
Патент 2655444 C1 РФ. МПК C07J 9/00, C07J 75/00. Способ выделения фитостеринов из таллового пека: № 2017131803: заявл. 11.09.2017: опубл. 29.05.2018 / И.Н. Чернов, А.О. Коршунов, Т.И. Долинский, М.А. Лазарев, Е.А. Маврина, И.С. Ильичев, А.Б. Радбиль. Chernov I.N., Korshunov A.O., Dolinskij T.I., Lazarev M.A., Mavrina E.A., Ilichev I.S., Radbil A.B. Method for the Isolation of Phytosterols from Tall Pitch. Patent RF no. RU 2655444 C1, 2018.
Barriuso B., Ansorena D., Astiasaran I. Oxysterols Formation: A Review of a Multifactorial Process. The Journal of Steroid Biochemistry and Molecular Biology, 2017, vol. 169, pp. 39–45. DOI: https://doi.org/10.1016/j.jsbmb.2016.02.027
Candioti L.V., De Zan M.M.D., Cámara M.S., Goicoechea H.C. Experimental Design and Multiple Response Optimization. Using the Desirability Function in Analytical Methods Development. Talanta, 2014, vol. 124, pp. 123–138. DOI: https://doi.org/10.1016/j.talanta.2014.01.034
Derringer G., Suich R. Simultaneous Optimization of Several Response Variables. Journal of Quality Technology, 1980, vol. 12, iss. 4, pp. 214–219. DOI: https://doi.org/10.1080/00224065.1980.11980968
Fernandes P., Cabral J.M.S. Phytosterols: Applications and Recovery Methods. Bioresource Technology, 2007, vol. 98, iss. 12, pp. 2335–2350. DOI: https://doi.org/10.1016/j.biortech.2006.10.006
Holmbom B., Erä V. Composition of Tall Oil Pitch. Journal of the American Oil Chemists’ Society, 1978, vol. 55, iss. 3, pp. 342–344. DOI: https://doi.org/10.1007/BF02669926
Laakso P.H. Determination of Plant Stanols and Plant Sterols in Phytosterol Enriched Foods with a Gas Chromatographic-Flame Ionization Detection Method: NMKL Collaborative Study. Journal of AOAC INTERNATIONAL, 2014, vol. 97, iss. 4, pp. 1097–1108. DOI: https://doi.org/10.5740/jaoacint.14-011
Montgomery D.C. Design and Analysis of Experiments. Wiley, 2013. 752 p.
Rudzinska M., Przybylski R., Zhao Y.Y., Curtis J.M. Sitosterol Thermo-Oxidative Degradation Leads to the Formation of Dimers, Trimers and Oligomers: A Study Using Combined Size Exclusion Chromatography/Mass Spectrometry. Lipids, 2010, vol. 45, iss. 6, pp. 549–558. DOI: https://doi.org/10.1007/s11745-010-3433-0
Shoichi Y. Method for Recovering Non-Saponified Product from Tall Oil Pitch and Method for Producing Sterols. Patent JP no. JP 2002194384 A, 2002.
Swamy G.J., Sangamithra A., Chandrasekar V. Response Surface Modeling and Process Optimization of Aqueous Extraction of Natural Pigments from Beta Vulgaris Using Box-Behnken Design of Experiments. Dyes and Pigments, 2014, vol. 111, pp. 64–74. DOI: https://doi.org/10.1016/j.dyepig.2014.05.028
Ullah I., Ahmad M.I., Younas M. Optimization of Saponification Reaction in a Continuous Stirred Tank Reactor (CSTR) Using Design of Experiments. PJEAS, 2015, vol. 16, pp. 84–92.
Zinkel D.F., Russell J. Naval Stores: Production, Chemistry, Utilization. New York, Pulp Chemicals Association, 1989. 1060 p.
