A Network of Processes for Biorefining Burdock Seeds and Roots.

In this work, a novel sustainable approach was proposed for the integral valorisation of Arctium lappa (burdock) seeds and roots. Firstly, a preliminary recovery of bioactive compounds, including unsaturated fatty acids, was performed. Then, simple sugars (i.e., fructose and sucrose) and phenolic compounds were extracted by using compressed fluids (supercritical CO2 and propane). Consequently, a complete characterisation of raw biomass and extraction residues was carried out to determine the starting chemical composition in terms of residual lipids, proteins, hemicellulose, cellulose, lignin, and ash content. Subsequently, three alternative ways to utilise extraction residues were proposed and successfully tested: (i) enzymatic hydrolysis operated by Cellulases (Thricoderma resei) of raw and residual biomass to glucose, (ii) direct ethanolysis to produce ethyl levulinate; and (iii) pyrolysis to obtain biochar to be used as supports for the synthesis of sulfonated magnetic iron-carbon catalysts (Fe-SMCC) to be applied in the dehydration of fructose for the synthesis of 5-hydroxymethylfurfural (5-HMF). The development of these advanced approaches enabled the full utilisation of this resource through the production of fine chemicals and value-added compounds in line with the principles of the circular economy.

Epoxidation of Methyl Esters as Valuable Biomolecules: Monitoring of Reaction.

The paper is focused on the epoxidation of methyl esters prepared from oil crops with various profiles of higher fatty acids, especially unsaturated, which are mainly contained in the non-edible linseed and Camelina sativa oil (second generation). The novelty consists in the separation and identification of all products with oxirane ring formed through a reaction and in the determination of time course. Through the epoxidation, many intermediates and final products were formed, i.e., epoxides with different number and/or different position of oxirane rings in carbon chain. For the determination, three main methods (infrared spectroscopy, high-pressure liquid chromatography and gas chromatography with mass spectrometry) were applied. Only gas chromatography enables the separation of individual epoxides, which were identified on the base of the mass spectra, molecule ion and time course of products. The determination of intermediates enables: (i) control of the epoxidation process, (ii) determination of the mixture of epoxides in detail and so the calculation of selectivity of each product. Therefore, the epoxidation will be more environmentally friendly especially for advanced applications of non-edible oil crops containing high amounts of unsaturated fatty acids.

The use of cosolvents in heterogeneously and homogeneously catalysed methanolysis of oil.

The paper describes transesterification of oil by methanol with use of cosolvents such as ethyl acetate, tetrahydrofuran, hexane, acetone and diethyl ether at catalyst homogeneous (potassium hydroxide) and heterogeneous (mixed oxides). The cosolvents dissolve oil and methanol to form a single (homogeneous) phase, which increases the reaction rate. Therefore, the biodiesel production will be environmentally friendly because less energy is consumed, which increases sustainability. The whole binodal curve of ternary plots of oil, methanol and cosolvent was determined to find the molar ratio, in which the reaction mixture forms a single phase. The ethyl acetate and tetrahydrofuran have relatively small heterogeneous region, because of the similarity of their electric dipole moment with methanol. After transesterification, the detailed analysis of ester and also glycerol phase was carried out. For homogeneous catalyst, the highest esters content in the ester phase was achieved with tetrahydrofuran. For heterogeneous catalyst, the ester content was lower with cosolvent than without cosolvent, probably due to dilution of reaction components by cosolvent or bonding of cosolvent to the active sites of the catalyst.

Butanolysis: Comparison of potassium hydroxide and potassium tert-butoxide as catalyst for biodiesel preparing from rapeseed oil.

Biodiesel is a mixture of esters of fatty acids (most often palmitic, stearic and oleic) and lower alcohols (in our work butanol) produced by transesterification. It is a renewable source of energy, prepared from triacylglycerides, which are contained in vegetable oils and animal fats. This work focuses on alkaline catalyzed transesterification of rapeseed oil with butanol and comparison of two catalysts (potassium hydroxide and potassium tert-butoxide). In industry is usually transesterification of rapeseed oil carried out like reaction catalyzed by potassium hydroxide. Potassium hydroxide have high content of K2CO3, KHCO3 and water. Moreover water is formed by neutralization of potassium hydroxide with free fatty acids contained in oil. In cause of tert-butoxide catalyzed reaction, it is not possible because tert-butoxide have not a OH- aniont, which is needed for water forming. The influence of various conditions (addition of water, temperature of separation, intensity of stirring and type of catalyst) on butanolysis process was studied for both catalysts. For both catalysts dependence of conversions on time were plotted. When tert-butoxide was used, satisfactory phase separation was not achieved. The only way was separation of hot crude reaction mixture without adding water. Ester formed by this method had high content of free glycerol and soaps, but reached higher conversion. The best results were obtained with KOH and subsequent separation of cold crude reaction mixture with the addition of water and slow stirring. The difference between reactions catalyzed by potassium hydroxide and potassium tert-butoxide was described.

Effect of phase separation temperature on ester yields from ethanolysis of rapeseed oil in the presence of NaOH and KOH as catalysts.

The effects of phase separation temperatures (5-90°C) on losses of higher fatty acid (C(16) and C(18)) ethyl esters in the glycerol phase were investigated. Losses of ethyl esters produced from ethanolysis of rapeseed oil were 30-60% higher when NaOH rather than KOH was used as homogeneous catalyst. The losses decreased with an increase in separation temperature, resulting in an increase in the yield of the ester phase. The concentration of impurities (e.g. alkali metals, free glycerol and glycerides) in the ester phase increased with increasing separation temperature due reversible transesterification and reciprocal solubility of the compounds. Carbonates formed during neutralization of the catalysts are also transesterification catalysts and they cause reverse reaction. The ethyl ester bound in the glycerol phase during NaOH-mediated catalysis can be extracted by heating the separated glycerol phase to 60-90°C. The ester yield is increasing with increasing separation temperature, however with decreasing quality.

Determination of esters in glycerol phase after transesterification of vegetable oil.

In biodiesel production, glycerol is formed as a side product and it is contained in the glycerol phase. This phase contains (besides glycerol): water, soaps, alcohol, traces of catalyst and glycerides and the remaining esters. In this paper, a new method for the determination of esters in the glycerol phase is introduced. The determination enables the minimization of the losses of biodiesel within the production process. It is based on the gradient RP-LC method (water and acetonitrile) with refractometric detection. The analysis is easy and the samples do not need any treatment (only dilution by water) and has a low detection limit. The results of this method were compared with the results of two other published methods: isocratic HPLC and GC. The disadvantage of these two methods is that they need extensive treatment of the sample, which takes many hours, and they are able to determine only the sum of esters. The new method is reliable, much faster and able to differentiate esters of almost each higher fatty acid (e.g. linoleic, linolenic, strearic alkyl ester) in the glycerol phase.

Relationships among flash point, carbon residue, viscosity and some impurities in biodiesel after ethanolysis of rapeseed oil.

Many samples of rapeseed oil ethyl ester were prepared by alkaline-catalyzed transesterification at various conditions (reaction time, temperature, amount of catalyst, the molar ratio of ethanol to oil, the rotations of a disperser and the purification by water). The concentrations of the key impurities for biodiesel quality (the concentrations of monoglycerides, diglycerides, triglycerides, free glycerol, ethanol, free fatty acids, water) and some qualitative parameters (flash point, carbon residue, kinematics viscosity at 40 degrees C) were determined and then the relationships among them were found out. The relationships were characterized by the linear or non-linear statistical models. The found models enable the better understanding of the significance of the qualitative parameters and estimate them from the concentrations of impurities. The temperature dependence was also measured in the case of the viscosity of ethyl ester and used rapeseed oil.

Combined effect of water and KOH on rapeseed oil methanolysis.

This paper deals with the effect of water and catalyst (KOH) amount on the quantity and quality of transesterification products of rapeseed oil by methanol, the methyl ester phase (i.e. yield, conversion), and the side-product, the glycerol phase (i.e. density, viscosity, the mass fraction of glycerol, esters, soaps). The dependencies were described by statistical models. The transesterification was carried out at constant reaction conditions (90 min reaction time, 400 rpm, 60 degrees Celsius). Twelve experiments with the independent factors, amount of potassium hydroxide (0.65-0.9 mg per gram of oil) and total amount of water (0.24-1.42 mg per gram of oil) naturally present in the reaction components or formed by the neutralisation reaction of free fatty acids and of added water. The data were analyzed by linear regression with respect to regression triplet (complex critical analysis of the model, data and regression method). The analysis resulted in a set of linear and/or quadratic models consisting of statistically proven terms at a statistical significance level of 0.05 and demonstrated that ester in the glycerol phase increases with increasing amount of soaps.

Ethanolysis of rapeseed oil - distribution of ethyl esters, glycerides and glycerol between ester and glycerol phases.

The distribution of ethyl esters, triglycerides, diglycerides, monoglycerides, and glycerol between the ester and glycerol phase was investigated after the ethanolysis of rapeseed oil at various reaction conditions. The determination of these substances in the ester and glycerol phases was carried out by the GC method. The amount of ethyl esters in the glycerol phase was unexpectedly high and therefore the possibility of the reduction of this amount was investigated. The distribution coefficients and the weight distributions of each investigated substance were calculated and compared mutually. The distribution coefficients between the ester and glycerol phase increase in this sequence: glycerol, monoglycerides, diglycerides, ethyl esters, and triglycerides. Soaps and monoglycerides in the reaction mixture cause a worse separation of ethyl esters from the reaction mixture. The existence of a non-separable reaction mixture was observed also, and its composition was determined.

Study of effects of some reaction conditions on ethanolysis of rapeseed oil with dispergation.

The alkaline-catalyzed (KOH) ethanolysis of rapeseed oil with the help of a mechanical disperser was researched in this study. The effects of chosen reaction conditions (independent variables: the reaction temperature and time, the amount of catalyst, the molar ratio ethanol to oil and the rotation frequency of the disperser) on the ethanolysis process and ways for the improvement of the transesterification and separation process were studied. The transesterification of oil, the separation of the ester phase from the glycerol phase and qualitative properties of the ester phase were monitored by many dependent variables (e.g. the yield of the ester phase, the weight concentration of glycerides, the content of potassium ions, etc.). The measured data was analyzed by multi-linear regression with the help of many statistical tests (significance of parameters, exclusion of outliers, etc.). The created mathematical models describing the relations between the independent and dependent variables were verified by several independent experiments.

The effect of the acidity of rapeseed oil on its transesterification.

The aim of this work is to study the transesterification of vegetable oil with a high acid number at unchanged reaction conditions. Rapeseed oil was used as the raw material and its acid number was changed by the addition of oleic acid (from 0.89 to 12.25 mg KOH/g). Methanol was used for transesterification (molar ratio of oil to methanol 1:6) and potassium hydroxide was used as a catalyst. After the reaction time, the residue of the catalyst was neutralised by gaseous carbon dioxide and the methanol excess was removed. After the separation of two phases, each of them was analyzed (in the ester phase: yield, content of methyl ester and acid number; in the glycerol phase: yield, density, viscosity, content of glycerol, soaps, methyl ester, potassium carbonate and hydrogen carbonate). The obtained data was compared with theoretical material balances and the effect on the saponification of oil was discussed. The results show that the yield of methyl ester (biodiesel) is significantly affected by a higher acid number, as well as enhanced soap formation. On the other hand, the conversion of the oil and acid number of the ester phase remain at constant values in studied borders.