METHOD FOR SYNTHESIS OF DEEP EUTECTIC SOLVENTS FROM PALM OIL EMPTY FRUIT FRUIT WASTE AND USED WASTE OIL

Abstract

This invention concerns Deep Eutectic Solvents (DES) based on palm oil empty fruit bunch waste and used cooking oil which are synthesized in several stages, namely the hydroxylation process of used cooking oil to obtain polyols, extraction of potassium carbonate from palm oil empty fruit bunch ash, synthesis of DES by mixing the results of potassium carbonate extraction from palm oil empty fruit bunch ash and polyol from used cooking oil hydroxylation, then applied to the process of making biodiesel from Crude Palm Oil (CPO). The purpose of this invention is to utilize solid waste from the palm oil industry and waste cooking oil, and to develop environmentally friendly solvents that can be used economically and can meet the needs of catalysts in the oleochemical industry in Indonesia. The results of FTIR and NMR tests show that the synthesized DES is proven to contain -OH groups and shows a proton relationship. The resulting DES is liquid without any sediment and is colorless.The synthesized DES is capable of producing biodiesel with a high yield value and meets biodiesel quality standards.

Description

DEEP EUTECTIC SOLVENTS (DES) BASED ON EMPTY FRUIT BUNCH WASTE PALM OIL AND WASTE-COOKED OIL AS CATALYST IN THE PRODUCTION OF BIODIESEL Invention Engineering Field This invention concerns Deep Futectic Solvents (DES) based empty palm oil fruit bunches waste and used cooking oil as catalyst in the biodiesel manufacturing process. More specifically, This invention relates to the effectiveness of Deep Futectic Solvents (DES) as a catalyst in the process of making biodiesel from crude Palm Oil (CPO). Background of the Invention This invention has been known as Deep Eutectic product. Solvents (DES) and are used to meet the needs of catalysts and environmentally friendly solvents in the oleochemical industry. Technological inventions related to Deep Futectic Solvents (DES) have also been disclosed as provided in Patent Number S002021122176 dated December 29, 2021 with the title Deep Futectic Solvent (DES) Based Potassium Carbonate and Glycerol as Catalysts for Biodiesel Production, where it was revealed that the use of potassium carbonate-based DES effective for use as a catalyst, proven by product test results which meets all SNI biodiesel quality parameters. The invention others as disclosed in patent number S00202402705 March 24, 2024 with the title Deep Futectic Synthesis Method Solvents (DES) from Used Cooking Oil as Raw Materials in Degumming of Crude Palm Oil, where it is revealed that the waste used cooking oil can be a source of renewable polyols and DES The synthesis results can remove gum from crude palm oil up to 925. However, the invention mentioned above still has Weaknesses and limitations include DES which are synthesized using commercial chemical raw materials supply depends on market availability. Furthermore, the proposed invention is intended to overcome the problems stated above by means of producing DES catalysts from empty oil palm bunch waste and used cooking oil to be applied in the manufacturing process biodiesel, where the catalyst raw material is easily obtained from solid waste from the palm oil industry and cooking oil waste. Brief Description of the Invention The main objective of this invention is to overcome pre-existing problems, especially in industry biodiesel that uses catalysts from chemical raw materials commercial. Deep Eutectic Solvents (DES) based on fruit bunch waste palm oil waste and used cooking oil as catalysts in the process the manufacture of biodiesel according to invention 1 consists of several stages, namely: a. hydroxylation process of used cooking oil to obtain polyol, b. extraction of potassium carbonate from ash empty oil palm bunches, c. DES synthesis by mixing results of potassium carbonate extraction from empty oil palm bunch ash and polyols from the hydroxylation of used cooking oil. Mixture homogenized and separated using a separating funnel until the bottom layer is produced which is characterized by a clear liquid without sediment, stable, and homogeneous. Another objective of this invention is to utilize waste solid palm oil industry and cooking oil waste, as well as for develop environmentally friendly solvents that can be used economically and can meet the catalyst needs of industry oleochemicals in Indonesia. Preferably, the synthesized DES with a molar ratio of 1:2 is has a density of 1.050 g / mL: viscosity of 1.186 cSt: and pH of 1.45. DES synthesized with a molar ratio of 1:2 can produce biodiesel from crude palm oil with a yield of 96.408 and in accordance with biodiesel quality standards. Short Description of Image Figure 1 is a flow diagram of the DES-based manufacturing process. empty palm oil bunch waste and used cooking oil. Figure 2, is a DES product based on empty coconut bunch waste. palm oil and used cooking oil. Figure 3, is the infrared spectrum of DES. Figure 4, is the !H and NOESY NMR spectrum of DES Figure 5 is a flow diagram of the biodiesel manufacturing process. by using DES catalyst based on empty fruit bunch waste palm oil and used cooking oil. Complete Description of the Invention This invention will be fully described with reference to to the accompanying figures. Referring to Figure 1, which shows a flow diagram of the DES manufacturing process based on empty palm oil fruit bunches and used cooking oil, which consists of several stages, namely: 1) Hydroxylation of used cooking oil by heating 300 mL of oil used cooking oil at a temperature of 40”C, then formic acid (908) is added as much as 412 mL and hydrogen peroxide (508) as much as 38 mL. The reaction temperature was maintained at 40”C for 1.5 hours, then separated and purified on the polyol from the mixture. i1) Extraction of potassium carbonate from coconut empty bunch ash palm oil, by dissolving 50 grams of ash that has been oven-dried at a temperature of 1059C into 250 mL of distilled water, then heated and stirred for 4 hours. The mixture was filtered using filter paper. filter. 111i) Synthesis of DES by mixing the results of potassium extraction carbonate from empty oil palm bunch ash and polyol from hydroxylation of used cooking oil with a molar ratio variation of 1:2, 1:3, 1:5, 1:7, and 1:9. The mixture was homogenized for 3 hours. at a stirring speed of 300 rpm and a temperature of 80”C, then separated using a separating funnel until a layer is produced / bottom characterized by clear liquid without sediment, stable and homogeneous. Referring to Figure 2, which shows the DES product based on empty palm oil fruit bunches and used cooking oil. DES products are successful if they produce a clear solution without sediment with density and viscosity analysis results must be far above the density of the compound forming it. DES synthesized analysis was carried out to determine its physical and chemical properties, such as density, viscosity, and pH tests, which can be seen in Table 1. Table 1. Results of Physical and Chemical Characterization of DES DES Molar Ratio Density (g / mL) Viscosity (cSt) pH 1:2 1,050 1,186 1,45 1:3 1.054 1.249 1.43 1:5 1.078 1.249 1.18 1:7 1,087 1,761 1.1 1:9 1,089 1,711 1,28 Referring to Table 1, it can be seen that DES has a value density and viscosity above the density of used cooking oil as the compound forming it, namely 0.90 g / mL, so it can be used as as a solvent and catalyst. The pH value of the resulting DES is low, namely pHX7, so DES can be used as acid catalyst in the biodiesel manufacturing process. As explained by Ching et al. 2007 in the Journal of Molecular Catalysis volume 267 with the title “12-Tungstophosphoric Acid Supported on MCM-41 for Esterification of Fatty Acid Under Solvent-Free Condition”, the high level of acidity of a catalyst also contributes increase its catalytic activity to accelerate the reaction rate in the biodiesel production reaction. Functional group analysis using FTIR test was also carried out to see the structural changes that occur and hydrogen bonds which is formed between the anion in potassium carbonate and the group hydroxyl on polyols. Referring to Figure 3, which shows infrared spectrum on DES, shows that there is interaction hydrogen bonds in DES. DES with ratios of 1:2, 1:3, 1:5, 1:7, and 1:9 has a consecutive wave number of 3354.16 cm 1, 3356.92 cm1!,3368.75 cm!, 3369.98 cm, 3362.77 cm!, which is read as an -OH group. Analysis of molecular structure and dynamics by NMR test spectroscopy on !H and NOESY spectra were also performed on DES. The !H NMR spectrum is carried out to obtain an overview of the type, number, and structure of DES molecules. Referring to Figure 4, the The chemical shift !H spectrum (0 ppm) of DES reads at 1.239: 1.277: 1.28: 1.38: 3.868: 3.959: and 4.142 as alcohol. While at a shift of 1.446 it is read as carbonyl, which is one H atom. bonded to carbon. NOESY NMR analysis was performed to produce data that shows the relationship of protons in molecules DES. Referring to Figure 4, in NOESY NMR the relationship can be observed protons in the DES molecule in two dimensions. A mixture of potassium carbonate and polyol in the eutectic composition, there is an interaction between the protons of the potassium carbonate group and the protons of the polyol group. Referring to Figure 5, which shows a flow diagram of biodiesel production process using DES-based catalyst empty palm oil fruit bunch waste and used cooking oil, which consists of from several stages, namely: 1) Homogenize methanol and DES catalyst (48 w / w against CPO) at a temperature of 50”C. il) Simultaneous transesterification with DES catalyst which is acid was carried out with a molar ratio of methanol:CPO, namely 20:1 for 2.5 hours at a temperature of 120°C and a stirring speed of 400 rpm. 111) The mixture is separated using a separating funnel with layers above is methyl ester (biodiesel). Biodiesel is produced in liquid and colored form yellow, analysis was carried out to determine the physical properties and chemical properties, such as density, viscosity, and pH tests, which can seen in Table 2. Table 2 Results of Physical and Chemical Characterization of Biodiesel Molar Ratio | Density | Yield Viscosity pH catalyst Catalyst (g / mL) (cst) (5) DEC 1:2 0.857 5.391 96.40 10.79 DEC 1:3 0.881 5.121 92.30 10.74 DEC 1:5 0.868 5.049 93.38 9.12 DEC 1:7 0.873 5.210 81.36 11.55 DEC 1:9 0.865 4.894 94.93 9.44 Sulfuric Acid 0.859 4.220 86.94 10.19 SNI 7182:2015 0.85-0.89 2, 3-6.0 ASTM D6751-09 - 1.9-6.0 EN 14214 0.86-0.9 — Referring to Table 2, it can be seen that the density and The viscosity of the biodiesel produced is in the range of values based on biodiesel quality standards. The biodiesel yield obtained quite high, namely above 908, with the highest yield obtained on the use of DES with a molar ratio of 1:2. This shows that DES is based on waste from empty palm oil bunches and oil used cooking oil is capable and effective in producing biodiesel with a value high yield and in accordance with biodiesel quality standards. From the description above it is clear that the results of this invention can provides benefits to the oleochemical industry because it is practical and efficient, can be utilized economically and can meet catalyst needs in Indonesia.

Claims

Waste-based Deep Eutectic Solvents (DES) synthesis method empty palm oil bunches and used cooking oil consisting of from several stages, namely: 1) Hydroxylation of used cooking oil by heating 300 mL used cooking oil at a temperature of 40”?C, then acid is added formate (908) as much as 412 mL and hydrogen peroxide (508) as much as 38 mL. The reaction temperature was maintained at 40”C for 1.5 hours, then separated and carried out purification of polyols from their mixtures. i1) Extraction of potassium carbonate from coconut empty bunch ash palm oil, by dissolving 50 grams of ash that has been oven at a temperature of 1059C into 250 mL of distilled water, then heated and stirred for 4 hours. The mixture was filtered using filter paper. i1i) Synthesis of DES by mixing the results of potassium extraction carbonate from empty oil palm fruit bunch ash and polyol from hydroxylation of used cooking oil with varying ratios molars 1:2, 1:3, 1:5, 1:7, and 1:

9. Mixture homogenized for 3 hours at stirring speed 300 rpm and a temperature of 80”C, then separated using separating funnel until a bottom layer is produced characterized by a clear liquid without sediment, stable, and homogeneous. The best synthesized DES in claim 1, is found in the ratio molar ratio of 1:2 which has a density of 1.050 g / mL, viscosity of 1.186 cSt, and pH 1.

45. The DES synthesized in claim 1 can produce biodiesel from crude palm oil with a yield above 908 and in accordance with biodiesel quality standards.