Effect of Increased Ratio of Mol Pereaktan and Ratio Enzyme Rhizomuccor Meihei to Yield Coco Dilaurylamide - Politeknik Negeri Padang

  

Effect of Increased Ratio of Mol Pereaktan and Ratio Enzyme

Rhizomuccor Meihei to Yield Coco Dilaurylamide

Lidyana Reihan1, Hellen Fransiska2 , Eka Kurniasih3

  

1,2,3Politeknik Negeri Lhokseumawe, Indonesia

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Abstract - In Indonesia the demand for household needs is increasing, for example, such as cleaning products with surfactant base material

that serves as a dirt binder. The problem that arises today is that most petroleum-based surfactants (petrochemical surfactants), while the raw

materials are classified as resource consumable and environmentally unfriendly because this type of material is not easy to decompose.

Therefore, along with the development of technology, surfactants can now be produced with alternative raw materials derived from natural

resources that are environmentally friendly and sustainable because it is a renewable natural resources. The advantages of making surfactants

from natural raw materials are easily degraded, lower production costs, lower energy requirements and free from aromatic hydrocarbons.

Coco dilaurylamide is one of the alkanolamide surfactants that act as a stabilizer and a foam developer. Coco dilaurylamide is the name given

to surfactants obtained from methyl laurate (C ^{11 H 23 COOCH 3 ) reactions with diethanolamine using pure coconut raw material (VCO) in an}

esterification reaction, wherein the VCO contains high lauric acid. The surfactant synthesis of pure coconut oil (VCO) was carried out through

the esterification stage at 65 C using a H2SO4 (10% v/v) catalyst for 2 hours. After esterification stage, followed by amidation stage using

Rhizomucor meihei enzyme biocatalyst with ratio 0,1%, 0,2%, 0,3%, 0,4%, 0,5% (w/w) and mole ratio methyl laurate Diethanolamine 1: 1, 1:

2, 1: 3, 1: 4, 1: 5 (w/v) at 500C for 4 hours. From the result of research of statistical data of variance analysis (ANAVA) it is known that the

increase of mole ratio of pereaktan and the increase of Rhizomucor meihei enzyme ratio significantly influence the yield of coco dilaurylamide.

Coco dilaurylamide with the highest yield has a pH value of 10, specific gravity (SG)1.08 and a boiling point of 85 C.

  Keywords : Coco dilaurilamide, Rhizomucor meihei, Aromatic hydrocarbon, Petrolem

  INTRODUCTION

  Imports of surfactants in Indonesia are increasing RESEARCH METHODOLOGY every year in line with the development of cleaning industry, Material cosmetic industry, food industry, textile industry and paint The materials used for the esterification process are industry.

  VCO, methanol, H SO . While the ingredients used for the

  2

  4 Coco dilaurylamide is a fatty amide groupcompound enzymatic amidation process are methyl laurate from VCO, and is a non-ionic surfactant widely used as a material for diethanolamine and Rhizomucor meihei biocatalyst.

  making shampoos, bath foams, latex feeders, rust inhibitors, household cleaning products and liquid detergents. Raw material for surfactant coco dilaurylamide is methyl laurate .Esterification of Pure Coconut Oil (VCO) with diethanolamine derived from vegetable oil. Diluted 65 ml of methanol with 200 ml VCO using

  One of the most widely used surfactants is coco H2SO4 (10% w/v) catalyst in the flask. Adjusted operating dilaurylamide. The use of this surfactant aims to improve the temperature at 65 C. Then separated methyl laurate with stability of the emulsion by lowering the surface tension, glycerol using separating funnel, then added NaOH into between the oil phase and the liquid phase. methyl laurate to neutralize pH. Reaction is done for 2 hours.

  Coco dilaurylamide produced by the enzyme Then added H

  2 O to methyl ester to purify methyl laurate from Rhizomuccor meihei lipase enzyme is safer to use when glycerol.

  compared to coco dilaurylamide (chemical reaction). Therefore, in this study, the analysis of acid numbers using Amylate Enzymatic Methyl Laurate the titration method to determine the highest yield of coco This research begins by taking samples of raw dilaurylamide amidation reaction. In this research used 2 materials to analyze the initial acid numbers. Then dissolved (two) independent variable that is ratio of enzyme 50 grams of methyl laurate in a n-hexane solvent at a ratio of Rhizomuccor meihei (% w/ w) and ratio of methyl lauric 1: 2 (w / v) to a three-neck flask with a condenser and agitator. mole: diethanolamine (w / v). The optimum condition of the The use of solvents in the reaction is intended to increase the reaction is the result of the interaction of two independent homogeneity of mixed solutions. The selection of n-hexane as variables. solvent was based on some previous studies

  . It is known that n-hexane has a low toxicity for lipase of 69°C to evaporate the solvent. Coco solvent-free enzyme activity when compared to other organic solvents. dilaurylamide then analyzed the final acid number to After methyl laurate and n-hexan have been mixed, then the determine the yield of the product. The yield of coco diethanolamine is added according to the specified mole ratio. dilaurylamide product is calculated based on the difference Further heated by adding Rhizomucor meihei enzyme between the initial acid number (raw material) and the final biocatalyst into the three-neck flask. Stirring scale 3 for 4 product acid number divided by the initial acid number. hours (Kaptriyani, 2008).

  .

  Product Purification

  Purification is done by screening to separate crude coco dilaurylamide with enzyme. The soluble coco dilaurylamide in n-hexane is further distilled at a temperature

  Methanol : 65 ml

  

VCO ( 200 ml)

H

  2 SO 4 (10% w/v) o Temp : 65 C Ratio mole of methyl

  

Esterification

laurate : Time : 2 jam diethanolamine

  (1:1, 1:2, 1:3, 1:4, 1:5)

Methyl laurate

N-hexan 100 ml

(50 gram)

  Time: 4 jam Enzyme catalyst Rhizomucor meihei o (0,1%, 0,2%, 0,3%,

  

Amidation

Temp : 65 C o 0,4%, 0,5%)

  : 55 C reaction Stirring scale 3

Screening

Enzyme

  Crude Coco Dilaurilamide Distillation N-hexan Coco

  Analysis BA Analysis the best of Coco Dilaurilamide

  Spesifik Boiling HPLC, pH

Gravity point FT-IR, GC

  

Figure 1. Flow Diagram of Research

RESULTS AND DISCUSSION

  Coco dilaurilamide acts as a stabilizer and a foaming agent According to Holmberg, (2011) states the use of diethanolamide in shampoo formulas can prevent the occurrence of excessive oil removal process in the hair and the resulting product does not cause pain in the eyes, so it is suitable for use as a soap product and shampoo on baby. Therefore dilaurilamide can be used in shampoo and soap products.

  Coco Dilaurylamide

  The n-hexan solvent used in the synthesis of coco dilaurylamide aims to dissolve methyl laurate to dietanolamine. Based on a study by Rahman, (2003) that n- hexan, benzene and heptane are solvents which give good results in alkanolamide synthesis and n-hexane has inert properties so as not to reduce the product mixture. Therefore, in the synthesis of dilaurylamide the solvent used is n-hexan 1:2 to methyl laurate (w / v).

  Based on figure 2 and figure 3 above can be seen the effect of increasing the ratio of methyl lauric mole: diethanolamine to yield coco dilaurylamide, the effect of increased enzyme ratio to yield of coco dilaurylamide and interaction factor to yield of coco dilauryamide:

1. Relation of Pereaktan Mole Ratio and Enzyme Ratio to Coco Dilaurylamide Yield

  M ^{K e a n o f o n v e rs i} _{0,5 0,4 0,3 0,2 0,1} ^{70 68 66 64 62} _{60 58 56 1,00 0,50 0,33 0,25 0,20} ^{Rasio Enzim Rasio Mol Main Effects Plot (data means) for Konversi} Figure 2. Effect of Increase of Pereaktan Mol Ratio and Enzyme Ratio to Yield Coco Dilaurylamide ^{Rasio Mol M e a n 1,00 0,50 0,33 0,25 0,20 85 80 75 70 65 60 55 Rasio 0,3 0,4 0,5 Enzim 0,1 0,2 Interaction Plot (data means) for Konversi} Figure 3. Interactional Interaction Charts Against Yield

  Examining the effect of enzyme ratio to yield coco dilaurylamide will be tested hypothesis. Hypothesis:

  Research on the synthesis of coco dilaurylamide using Rhizomucor meihei enzyme was performed at 5 levels of biocatalyst ratio in percent weight (w / w) ie 0.1%; 0.2%; 0.3%; 0.4%; and 0.5% and 0% (non-enzyme) as the reaction control.

  Examining the interaction effect between factors to yield coco dilaurylamide will be tested hypothesis. Hypothesis: H0: (αβ) ij = 0 for all i, j (Interaction between factors does not affect the yield of coco dilaurylamide)

  Interaction Factor Against Yield Coco dilaurilamide

  From the statistical output, the enzyme F ratio was 322.06 and P by 0.000. The conclusion is to reject the initial hypothesis that increased enzyme ratio has no effect on yield of coco dilaurylamide. Hence the accepted alternative hypothesis which states increase in enzyme ratio effect on yield coco dilaurilamide.

  (Increased enzyme ratio has no effect on yield of coco dilaurylamide) H0: at least one βj ≠ 0 j = 1, 2, 3 (Increased enzyme ratio effect on yield of coco dilaurylamide)

  H0 : β1 = β2 = β3 = 0

  Effect of Enzyme Ratio on Coco dilaurylamide Yield

  Here is a graph generated from the Minitag Release 14 variance analysis program (ANAVA)

  From the statistical output, F mole ratios of 299.59 and P by 0.000. The conclusion is to reject the initial hypothesis that the increase in the mole ratio has no effect on the yield of coco dilaurylamide. Hence the accepted alternative hypothesis which states the increase in the mole ratio affects the yield of coco dilaurylamide.

  at least one αi ≠ 0 i = 1, 2, 3 (Increased mole ratio effect on yield of coco dilaurylamide)

  Experiments without the use of enzymes are aimed at knowing the magnitude of the effect that lipase can have on the reaction. The amidation reaction lasts for 4 hours at 50 ° C with a mole ratio of 1: 1, 1: 2, 1: 3, 1: 4, and 1: 5 between methyl laurate to dietanolamine.

  (Increased mole ratio has no effect on yield of coco dilaurylamide)

  H0 : α1 = α2 = α3 = 0

  Hypothesis:

  Effect of Mole Ratio Against Yield Coco Dilaurylamide E xamining the effect of mole ratio to yield of coco dilaurylamide will be tested hypothesis.

  H0

  FT-IR results also show that coco dilaurylamide is included in a surfactant having a water-like (hydrophilic) polar part because it contains a hydroxyl group (-OH). This is stated by Jatmika, (1998) surfactant generally composed of non-polar parts (lipophilic) is a long alkyl chain, while the polar part (hydrophilic) contains a hydroxyl group.

  85 o

  From the FT-IR analysis it is known that the coco dilaurylamide wave number of methyl laurate is at 1563.56cm-1 C = O and 1456,90 cm-1 C-N bonds. The results of this study coincide with Kurniasih, (2008) the number of dietanolamide waves in 1627.24 cm-1 bonds C = O and 1419,87 cm-1 bonds C-N

  Figure 6. Results of FT-IR Analysis

  From the analysis above characteristics can be seen that coco dilaurilamida and specific gravity produced boiling point has not approached the commercial product, this is because the product coco dilaurilamida has not undergone a purification process to separate coco dilaurilamide with ester methyl laurate which is not formed into coco dilaurilamida so that required process further purification to obtain a pure dilaurilamide product. As for the resulting pH has been in accordance with commercial products.

  10 SG 1,08 0,98 – 0,99

  10

  o C pH

  C 239

  Parameter Dilaurylamide (Synthesis) Commercial Boiling point

  H1: (αβ) ij ≠ 0 (Interaction between factors affect the yield of coco dilaurylamide)

  Based on the results of characteristic analysis, the best product of coco dilaurylamide found in the highest% acid drop rate can be seen in the following table: Table 1. Results of product characteristics analysis

  2.Characteristic of Coco Dilaurylamide Product

  From Gc analysis results can be seen that the ester content in methyl laurate is 2.2686%, the resulting ester content is still low but monoglyceride, digliserida has formed the performance of enzymes to break the bonds become esters become shorter. So dilaurilamida formation process does not require a long time and free fatty acid content has been reduced so as not to interfere with dilaurilamida product. This is one of the advantages of coco dilaurylamide synthesis using methyl lauric ester as raw material for making coco dilaurylamide. The remaining residual tiglyceride is 1.3031%, indicating the remaining tiglyceride that has not formed into esters.

  Figure 5. Results of GC Chomotographic Analysis (GC)

  Coco dilaurilamide produced still remains the ester, this is because the raw material of methyl laurate ester content is still low. The results of ester content on raw materials were confirmed using Chromosografi Gas (GC) analysis. Here are the results of ester content using Chromosografi Gas analysis (GC):

  The yield of coco dilaurylamide was confirmed using product component analysis using HPLC and obtained yield coco dilaurylamide at optimum condition of 98.76% with the remaining ester of 1.23%.

  Figure 4. HPLC Analysis Results

  From the statistical output, the mole ratio to the enzyme ratio is 16.52 and P is 0.000. The conclusion is that there is influence of mole ratio interaction to enzyme ratio significantly to coco dilaurylamide yield.

• – 244

  CONCLUSION 2012, Halaman xx-xx. Jurusan Teknologi Kimia Based on the results of the research and statistical dan Industri, Semarang.

  analysis of variance (ANAVA) a significant influence on yield was given by increasing the ratio of methyl lauric

  9. Rahman, A. M.B., Yap. C.l. K., Dzulkefly, dan Rahman,

  mole: diethanolamine and increased Rhizomucor meihei

  A. 2003. Synthesis of Palm Oil Alkanolamide Using enzyme ratio. Characteristics of coco dilaurylamide with the Lipase . Journal of Oleo Science (JOS) Vol 52 No.

  highest yield were: pH 10, specific graffiti (SG) 0.918 and 2, hal 65-72 boiling point 85 oC and FT-IR analysis showed coco dilaurylamide formed on wave 1563.56 cm-1 C = O and

  10. Reetz. 2002. Lipase Sebagai Biokatalis. Current 1456,90 cm- 1 CN bond.

  Opinion in Chemical Biology 6:145-150 Ilmiah, diakses Thank-you note 28 April 2017).

  T o Dikti who has funded this research and Basic Chemical

  & Analysis Laboratory and Unit Process Laboratory which has provided facilities in this research.

  REFERENCES

  1. Arbianti, Rita., Tania S.Utami. 2008. Pemanfaatan Biji Wijen Sebagai Sumber Enzim Lipase Untuk Reaksi esterifikasi Gliserol-Asam Laurat Pada Pembuatan Agen Pengemulsi. Prosiding Seminar Nasional Rekayasa Kimia dan Proses. ISSN : 1411-4216

  2. Arfah, Muh, Mappiratu dan Razak AR. 2015. Optikasi Reaksi Esterifikasi Asam Lurat Dengan Methanol Menggunakan Katalis Asam Sulfat Pekat. Jurnal vol. 4 No. 1, Maret 2015 : 46-48. Jurusan Kimia, Universitas Tadulako.

  3. Fatarina, Ery dan Bambang Pramudono. 2009. Pembuatan Surfaktan Polyoxyethylene Dari Minyak Sawit: Pengaruh Rasio Mono-digliserida Dan Polyethylenglykol. Jurnal Vol. 12 No. 3, Juni 2009, Hal. 175-182. Jurusan Teknik Kimia, Semarang.

  4. Holmberg, K. 2001. Natural Surfactants, Colloid & , 6 : 148 Interface Science – 159.

  5. Kurniasih, Eka. 2008. Pemanfaatan Asam Lemak Sawit Destilat Sebagai Bahan Baku Dietanolamida Menggunakan Enzim Lipase (Rhizomucor meihei). Jurusan Teknik Kimia, Medan.

  6. Kurniasih, Eka dan Tjahjono Herawan. 2013. Optimasi Reaksi Amidasi Enzimatis Dietanolamida Menggunakan Rhizomucor meihei. Jurusan Teknik Kimia, Lhokseumawe.

  7. Kaptriyani, Marina. 2008. Pemanfaatan Gliserol Hasil Samping Pabrik Biodiesel dan Destilat Asam Lemak Sawit Sebagai Emulsifier Monopalmitat Secara Enzimatis. Tesis. Universitas Sumatera Utara

  8. Probowati, Astri, Paradigma Cario Geovani dan Diyono Ikhsan. 2012. Pembuatan Surfaktan Dari Minyak Kelapa Murni (VCO) Melalui Proses Amidasi Dengan Katalis NaOH. Jurnal Vol. 1 No. 1, Tahun