Synthesis of Emulsifier from Refined Bleached Deodorized Palm Stearin by Chemical Glycerolysis in Stirred Tank Reactor
Abstract
Emulsifiers are widely used in the food and beverage industry, especially the mixture of mono- and diacylglycerol. They are produced from glycerolysis reaction using chemical catalysts because of fast reaction time, high conversion of reactants and low cost. Palm stearin is abundant and less utilized. Therefore, palm stearin is used as raw material for the synthesis of emulsifiers. The goal of this project was obtained emulsifier containing high concentrations of mono- and diacylglycerol. Synthesis of emulsifier was conducted with reaction time (1 h to 12 h), catalyst concentration (1 %, 2 %, 3 %, and 4 %) (w/w) and addition of molecular sieve (12 % (w/w) and without as control). Furthermore, products were fractionated at various temperatures (40 ∘C, 30 ∘C, 20 ∘C, and 10 ∘C). These results suggest that the best conditions for the synthesis of mono- and diacylglycerol from palm stearin using NaOH catalyst in Batch stirred Tank Reactor are NaOH concentration 3 % (w/w), reaction time 6 h, molecular sieves 12 % (w/w), reaction temperature 90 ∘C, addition of tert-butanol as solvent 2 mL ⋅ g −1 of oil, palm stearin: glycerol molar ratio (1 : 5), the speed of the stirrer of 400 rpm. The fractionation temperature is 30 ∘C with product yield is 61.43 % which contains 91.00 % ± 2.50 % and 9.00 % ± 2.50 % of monoand diacylglycerol, respectively. Characteristic of emulsifiers are emulsion capacity 95.55 % ± 0.71 %, emulsion stability 90.44 % ± 1.24 %, HLB value 10.25 ± 0.44, melting point 62.67 ∘C ± 2.52 ∘C to 70.33 ∘C ± 0.58 ∘C and type of emulsion is oil in water (o/w).
Keywords: Emulsifier, Glycerolysis, Mono- and diacylglycerol, NaOH, Palm stearin
References
[1] Hasenhuetti GL. Food emulsifiers and their application. Second Edition. Springer, Madison, Wisconsin; 2008. https://www.springer.com/gp/book/9780387752839
[2] Kaewthong W. Continuous production of monoacylglycerols by glycerolysis of palm olein with immobilized lipase. Journal of Process Biochemistry. Elsevier; 2005:40:1525–1530. http://pirun.ku.ac.th/$\sim$fagissi/research/PalmOlein/ monoacylglycerols.pdf
[3] Kimmel, T. Kinetic investigation of the base-catalyzed glycerolysis of fatty acid methyl esters [Thesis]. Faculty of Mathematics and Science. Technical Berlin University (2004). https://www.depositonce.tu berlin.de/handle/11303/1283
[4] Kamel BS. Emulsifiers. Food additive user’s handbook. J. Smith (ed.). Blackie Academic & Profesional, Glasgow, UK; 2004. http://gtu.ge/Agro-Lib/ [Fatih_Yildiz]_Advances_in_Food_Biochemistry(BookFi.org).pdf.
[5] Malaya KN, Naik SN, Monty S. Enzymatic glycerolysis for conversion of sunflower oil to food based emulsifiers. Catalysis Today. Science Direct 2014;237:145–149. https: //www.sciencedirect.com/science/article/pii/S0920586113006081
[6] Endalew AK, Kiros Y, dan Zanzir R. Inorganic heterogeneous catalysts for biodiesel production from vegetable oils. Biomass Bioenergy 2011;35(3):787–809. https:// www.sciencedirect.com/science/article/pii/S0961953411003357
[7] Harismawati A, Prasetyo F. Produksi mono dan digliserida dengan proses gliserolisis pseudohomogen dari minyak goreng bekas. [Production of mono and diglyceride with pseudohomogen glycolysis process from used cooking oil]. [Thesis]. Universitas Diponegoro (2008). http://eprints.undip.ac.id/36791/1/89.Jurnal_Penelitian.pdf [in Bahasa Indonesia].
[8] Boz N, Degirmenbasi N, Kalyon DM. Esterification and transesterification of waste cooking oil over amberlyst-15 and modified amberlyst-15 catalyst. INFONA 2015;165:723–730. https://www.infona.pl/resource/bwmeta1.element.elsevier319decf4-8fb1-3d22-b0ae-5c52faa2d076?locale=en
[9] Fan G. Liao C, Fang T, Luo S, Song G. Amberlyst-15 as a new and reusable catalyst for the conversion of cellulose into cellulose acetate. Carbohydrate Polymers. ResearchGate; 2014:112:203–209. https://www.researchgate.net/publication/263317417_Amberlyst_15_as_a_new_and_reusable _catalyst_for_the_conversion_of_cellulose_into_cellulose_acetate
[10] Jeenpadiphat S, Tungasmita DN. Acid-activated pillar bentonite as a novel catalyst for the esterification od high FFA oil. Powder Technology. CAB Direct 2013;237:634– 640. https://www.cabdirect.org/cabdirect/abstract/20143050468
[11] Suyin G, Hoon KN, Park HC, Fook LL. Heterogeneous free fatty acids esterification in waste cooking oil using ion-exchange resins. Infona; 2012:102:67–72. https://www.infona.pl/resource/bwmeta1.element.elsevier-d09ed0ea-da66-3b55- ae08-348840a840f3
[12] Yanuar, S.P. dan Mulyani, S. Proses gliserolisis CPO menjadi mono dan diasilgliserol dengan pelarut tert-butanol dan katalis MgO. [CPO glycolysis process into mono and diacylglycerol with butanol-tert-solvent and MgO catalyst] Universitas Diponegoro, Semarang; 2013. [in Bahasa Indonesia] http://eprints.undip.ac.id/3486/
[13] Ulfa A. Sintesis monoester gliserol asam palmitat menggunakan H2SO4 etanolatamberlyst-15 dalam stirrer tank reaktor. [Synthesis of Monoester Glycerol Palmitic Acid Using H2SO4 Ethanolate-Amberlyst-15 In Stirrer Tank Reactor] Universitas Gadjahmada; Yogyakarta (2015). [in Bahasa Indonesia]
[14] Sabeder S, Habulin M, Knez Z. Lipase-catalyzed synthesis of fatty acid. Elsevier 2006;77(4):880–886. https://www.sciencedirect.com/science/article/pii/ S0260877405005674?via%3Dihub
[15] Soheila Z, Sahari MA, Barzegar M, Esfehani ZH. Production of cocoa butter replacer by dry fractionation, partial hydrogenation, chemical and enzymatic interesterification of tea seed oil. Scirp 2012;3(2):184–189. http://file.scirp.org/Html/7- 2700318_17513.htm
[16] Zaelani, A. Sintesis Mono dan Diasilgliserol dari Refined Bleached and Deodorized Palm Oil. Departemen Ilmu dan Teknologi Pangan. [Synthesis of Mono and Diasilglycerol from Refined Bleached and Deodorized Palm Oil. Department of Food Science and Technology] Institut Pertanian Bogor; Bogor. 2007. https://anzdoc.com/skripsisintesis-mono-dan-diasilgliserol-dari-refined-bleach.html [in Bahasa Indonesia]
[17] Musthofa, C. Mempelajari proses pemekatan diasilgliserol dari fraksi kaya diasilgliserol dari hasil gliserolisis enzimatis refined bleached and deodorized palm oil. [Study of diacylglycerol concentration from diasilgliserol rich fraction of enzymatic glyceroline result refined bleached and deodorized palm oil,Skripsi]. Departemen
Ilmu dan Teknologi pangan. Institut Pertanian Bogor, Bogor; 2009. http://repository. ipb.ac.id/handle/123456789/11230 [in Bahasa Indonesia]
[18] Francisco J, Andrade, Jacob T, Shelley, William C, Wetzel, Michael R. Webb, Gerardo Gamez, Steven J, Ray, Gary M, Hieftje. 2008. Atmospheric pressure chemical ionization source 2. Desorption-ionization for the direct analysis of solid compounds. ACS Publication 2008;80(8):2654–2663. https://pubs.acs.org/doi/abs/ 10.1021/ac800210s
[19] Lopez DE, Goodwin JG, Bruce DA, Lotero E. Transesterification of triacetin with methanol on solis acid and base catalysts. Academia 2005;295;97–105. http://www.academia.edu/28685612/ Transesterification_of_triacetin_with_methanol_on_solid_acid_and_base_catalysts
[20] Kholifaturrosyidah F. Sintesis biosurfaktan ester fruktosa oleat secara enzimatis menggunakan lipase amobil pada matrik modifikasi hidrofobik dalam fluidized bed reactor. [Synthesis of enzymatic esther fructose oleic oleic synthesis using amobil lipase in a hydrophobic modification matrix in a fluidized bed reactor,Thesis] Department of Food Technology and Agricultural Products. Gadjah Mada University; Yogyakarta. 2014. http://etd.repository.ugm.ac.id/index. php mod=penelitian_detail&sub=PenelitianDetail&act=view&typ=html&buku_id= 78019&obyek_id=4 [in Bahasa Indonesia].
[21] Gupta RK, James K, Smith FJ. Sucrose ester and sucrose ester/glyceride blends as emulsifiers. Springer 1983;60:862. https://link.springer.com/article/10. 1007/BF02787451
[22] Winarno, F. G. Kimia pangan dan gizi. [The Chemical of food and nutrient] PT Gramedia Pustaka Utama, DKI Jakarta; 2002. http://onesearch.id/Record/IOS3341. siprus-00000000000000046021 [in Bahasa Indonesia].
[23] Vlada BJ, Ivana BB, Olivera SS. Purification of crude biodiesel obtained by heterogenously-catalized transesterification. ScienceDirect 2015;49:500–516. https: //www.sciencedirect.com/science/article/pii/S1364032115003676
[24] Margareth N, Purba RD, Ritonga MY. Pengaruh jumlah katalis abu cangkang telur ayam dan waktu reaksi gliserolisis pada pembuatan mono Dan diasilgliserol dengan menggunakan co-solvent tert-butanol. [Influence of amount of chopped egg shell catalysts and time of glycolysis reaction on preparation of mono and diasilglycerol by using a co-solvent tert-butanol] University of North Sumatra; Medan. 2014:3:43. http://download.portalgaruda.org/article.php?article=275631&val= 4138&title=PENGARUH%20JUMLAH%20KATALIS%20ABU%20CANGKANG% 20TELUR%20AYAM%20DAN%20WAKTU%20REAKSI%20GLISEROLISIS% 20PADA%20PEMBUATAN%20MONO%20DAN%20DIASILGLISEROL%20(MDAG)% 20DENGAN%20MENGGUNAKAN%20CO-SOLVENT%20%20TERT-BUTANOL [in Bahasa Indonesia].
[25] Zulfikar. Pengaruh kalsium karbonat dan gliserol terhadap produk gliserolisis refined bleached deodorized palm oil (RBDPO). [Effects of calcium carbonate and glycerol on refined bleached deodorized palm oil (RBDPO) glyceroline products] Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of North Sumatera. Medan. 2009. [in Bahasa Indonesia] http://repository.usu.ac.id/bitstream/ 123456789/13958/1/10E00367.pdf
[26] Widiyarti G, Hanafi M. Pengaruh konsentrasi katalis dan perbandingan molaritas reaktan pada sintesis senyawa alpha-monolaurin. [Effect of catalyst concentration and comparison of reactant molarity in synthesis of alpha-monolaurin Compounds] PUSPIPTEK, Serpong; Tangerang. 2008;12:2. https://ejournal.undip.ac.id/index.php/ reaktor/article/view/1509 [in Bahasa Indonesia].
[27] Kaewthong W. Continuous production of monoacylglycerols by glycerolysis of palm olein with immobilized lipase. Journal of Process Biochemistry. Elsevier 2005;40:1525–1530. https://www.sciencedirect.com/science/article/pii/ S0032959204000081?via%3Dihub
[28] Hingu SM, Gogate PR, Rathod VK. Synthesis of from waste cooking oil using sonochemical reactors. Europe PMC 2010;17:827−832. https://europepmc.org/abstract/ med/20303314
[29] Koh MY, Mohd TJ, Ghazi M. 2011. A review of production from jatropha curcas L. oil. IDEAS 2011;11:2240–2251. https://ideas.repec.org/a/eee/rensus/v15y2011i5p2240- 2251.html
[30] Wang R, Zhou WW, Hanna MA. Preparation, optimization and fuel properties from non-edible feedstock, datura stramonium L. fuel. Science Direct 2012;91:182−186. https://www.sciencedirect.com/journal/fuel/vol/91/issue/1
[31] Gunstone FD, Harwood JL, Padley FB. Lipid handbook. Chapman and Hall. 1995. https://onlinelibrary.wiley.com/doi/abs/10.1002/lipi.19950970720
[32] Fardiaz D. Pengaruh laju pendinginan, suhu dan lama kristalisasi terhadap profil triasilgliserol dan sifat melting produk fraksinasi minyak kelapa. [Effect of cooling rate, temperature and length of crystallization on triacylglycerol profile and melting properties of coconut oil fractionation products] Department of Food Science
and Technology. Faculty of Agricultural Technology. Bogor Agricultural Institute; Bogor. 2013;18:1. http://journal.ipb.ac.id/index.php/JIPI/article/view/8348 [in Bahasa Indonesia].
[33] O’Brien RD. Fats and Oils: Formulating and processing for applications. CRC, Boca Raton; 2004. https://www.crcpress.com/Fats-and-Oils-Formulating-and-Processingfor-Applications-Third Edition/OBrien/p/book/9781420061666
[34] Huey SM, Hock CC, Lin SW. Characterization of low saturation palm oil products after continuous enzymatic interesterification and dry fractionation. NCBI 2009;74:E177- E183. https://www.ncbi.nlm.nih.gov/pubmed/19490322 [35] Hariyadi MP, Purnomo EH, Andarwulan. Fraksinasi kering minyak kelapa menggunakan kristalisator skala 120 kg untuk menghasilkan fraksi minyak kaya triasilgliserol
rantai menengah. (Dry practionation of coconut oil using a 120 kg crystallizer scale to produce a rich oil fuel fraction triacylglycerol chain) IPB, Bogor; 2013:19(1):1–50 lhttps://repository.ipb.ac.id/handle/123456789/64111 [in Bahasa Indonesia].
[36] Timms RE. Fractional crystallisation – the fat modification process for the 21st century. European Journal of Lipid Science and Technology 2005;107(1):48-57. https://doi.org/ 10.1002/ejlt.200401075
[37] Calliuw G, Fredrick E, Gibon V, De Greyt W, Wouters J, Foubert I, Dewettinck K. On the fractional crystallization of palm olein: solid solutions and eutectic solidification. Food Research International 2010;43:972–981. https://lib.ugent.be/en/ catalog/pug01:979618