The esterification of lactic acid with ethanol over Lewatit S 100, strong cation ion exchange resin catalyst, was studied in counter current vapor-liquid contactor type differential reactor by feeding ethanol and lactic acid solution as vapor and liquid phases, respectively. The ethanol vapor phase was diluted by dry air and the water removal was achieved by the mass transfer of water from liquid to vapor phase. Effect of ethanol to lactic acid feed molar ratio and vapor flow rate on fractional conversion and water removal efficiency were tested at 40-70&deg / C of column temperature range. It was observed that Lewatit S 100 was adequate catalyst for esterification of lactic acid with ethanol. Increase in ethanol to lactic acid feed molar ratio enhanced both lactic acid conversion and water removal by upper product stream. However, lactic acid conversion was suppressed by the increase of inlet vapor flow rate because of the decrease in ethanol concentration in gas phase which affected both esterification reaction rate and mass transfer rate. The reaction temperature is the other important parameter that affects the mass transfer of ethanol from vapor to liquid phase. Although reaction rate and equilibrium conversion values were promoted by temperature, the lower solubility of ethanol in liquid phase limited the fractional conversion while promoted the water mass transfer from liquid to vapor phase. The optimized vapor phase velocity and temperature can yield higher conversions than the equilibrium conversion at the same temperature and initial composition. Therefore, low pressure organic acids such as lactic acid can be successfully esterified by using counter current V-L contactor type reactors and by using integrated reaction and separation units.

Ethyl lactate is a promising, and environmentally benign chemical, which requires efficient separation techniques to overcome the equilibrium limitations in its production. Pervaporation based hybrid systems are successful in these type of equilibrium limited reactions, where product and/or by-product are removed from reaction medium by pervaporation unit(s) so as to drive reaction to completion. For the production of ethyl lactate four possible semi-batch hybrid systems were previously proposed. However, in order to select the suitable hybrid system within the proposed layouts phase equilibrium and reaction kinetics of the system must be well defined in addition to the performance data of the pervaporation membranes. Therefore, vapor pressure curve of ethyl lactate, VLE curves of ethanol-ethyl lactate and ethyl lactate-water were determined and performances of commercial hydrophobic membranes were investigated experimentally for the separation of ethanol-ethyl lactate mixtures. As a result of vapor pressure and VLE experiments, azeotrope was observed at 71wt% of water for ethyl lactate-water binary mixture at 80mmHg pressure. Furthermore, dependence of vapor composition on pressure was found to be slight for ethanol-ethyl lactate mixtures. Two commercial hydrophobic membranes, and an organoselective one were used in the separation of ethyl lactate-ethanol mixtures. It is found that hydrophobic membranes have sufficient fluxes and reasonable selectivities. Moreover, it is observed that as temperature increase flux increases and selectivity decreases. Finally, it is concluded that it would be possible to produce ethyl lactate by using the previously proposed integrated PV-esterification reactor systems.

This diploma thesis deals with chemical recyclation polylactide to lactide. In the theory is summarized actual state of knowledge about chemical recyclation of polylactides, their properties, preparations a possibilities of characterization. Experimental part of work verify ethanolysis of PLA withthe samples of granulate, waste filaments and textiles. In the experimental work is suggested an optimalization of alcoholysis to direct yield of oligomer suitable for depolymerization to lactide. This method was verified for 5 different samples of PLA, which 4 of them was made of waste PLA. The time needed for depolymerization was evaluated and the effect of catalysis. Lactide and PLA recyclates was further analyzed by NMR, FTIR, DSC and GPC.

This master thesis deals with the synthesis of lactide from lactic acid esters. The theoretical part focuses on the current understanding of technology of lactic acid, its alkyl esters and the cyclic lactic acid dimer - lactide, which is mainly used as a precursor for the synthesis of high moleculat weight biodegradable polylactide (PLA) and other copolymers. Experimental part is then focused on the synthesis of lactide from lactic acid alkyl esters, especially ethyl lactate. Examines the design of a suitable apparatus for this synthesis and the application of the most appropriate reaction conditions (temperature, pressure, catalysis) to optimize the preparation of the desired product. In the end, parameters of prepared lactide are characterized by using of various analytical techniques.

The work focuses on new processes for the preparation of lactic acid derivatives. The main objective was to verify the feasibility of preparing high molecular weight polylactide using ethyl lactate as a precursor of lactide synthesis. Part of the work is devoted to the new ethyl lactate synthesis method. The experimental part of the thesis is divided into partial key steps on the way from the lactic acid to the high molecular polylactide. The preparation of anhydrous ethyl ester of lactic acid (EtLA) was solved in an innovative way using alcoholysis of the oligomeric lactic acid. A kinetic model for isothermal alcoholysis and equimolar reactants ratio was derived from this method. The ethyl lactate was oligomerized by transesterification into the low and high molecular weight oligomer with the help of newly found catalysts suitable for the reaction medium. Stannous lactate was used as catalyst for oligomerization of the low molecular weight polymer suitable for the preparation of lactide (Mn 1000 g.mol-1). Experimental polymerization of ethyl lactate into high molecular weight product in tens of kDa has been investigated with newly synthesized tetraethyllactoyl titanate, Ti(EtLA)4. The laboratory method was derived for the depolymerization of the oligomer into lactide. Optimal conditions found for lactidation are as follow: temperature 225 ° C, pressure 2 kPa, catalysis 0,05 mol% of stannous lactate (with respect to oligomer lactate units). The prepared lactide was refined to polymer grade purity by distillation and subsequent recrystallization from ethyl acetate and toluene. The method for the preparation of high molecular weight PLA through ROP polymerization of lactide has been optimized. By optimization, suitable catalyst concentration was found in combination with the polymerization temperature and the polymerization length. An equimolar mixture of Tin 2-ethylhexanoate and 1-decanol was used as the catalytic system. The optimal ROP conditions for achieving the maximum molecular weight and suppressed polymer coloration (yellowing) are: catalyst concentration 0,01 mol%, temperature 160 °C, and polymerization length 4 hours. PLA with molecular weight Mw= 447 ± 7,8 kg.mol-1 was prepared at these conditions and good repeatability of the result was achieved. The effect of naturally occurring lactide contaminants and their influence on the course and ROP result was experimentally verified on the optimized polymerization system. The purpose was to explore the effect of lactide contamination with water and ethanol as natural lactide contaminants. The results clearly confirm the orderly lower sensitivity of the polymerization system for the presence of ethanol as compared to water contamination. In the case of the presence of water, the course and the result of the polymerization in terms of both the conversion and achieved molecular weights are negatively affected, even when the water content is in the order of 0,001%. Conversely, the presence of ethanol has a positive effect on lactide conversion and polymer polydispersity. Lactides with an alcohol content of about one-tenth of a percent are suitable to reach molecular weights of PLA similar to commercially available products. This difference shoves a significant advantage in the proposed technology of preparing PLA from ethyl lactate, especially for easier purification of crude lactide into polymer grade purity.

This diploma thesis deals with senthesis of lactic acid ethyl ester from slats of lactic acid. The literature review has been processed in the theoretical part of the diploma thesis. It is focused on manufacturing technologies of lactic acid esters, mainly on ethyl lactate by conventional and non-conventional ways of producing. Also the literature review involves producing of lactic acid and slats of lactic acid by fermentation because subsequently is possible produce ethyl lactate from that two substances. The laboratory apparatus for preparation of ethyl lactate and methyl lactate has been designed, realized and verificated function of it in the experimental part. There were carried out laboratory experimnets for production ethyl lactate and methyl lactate in this apparaturs.

Ethyl lactate (EL) plays a major role as green solvent and also a replacement for most petrochemical solvents. The esterification process of lactic acid and ethanol to produce EL is an equilibrium-limiting reaction and the selective removal of one of the reaction products can be improved using a membrane reactor and when coupled with a heterogeneous catalyst offers an opportunity for process intensification. This thesis investigates the batch process esterification reaction involving lactic acid (LA) and ethanol (EL) in the presence of a water selective membrane using different cation-exchange resin catalysts. The product was analysed using gas chromatograph coupled with mass spectrometry detector (GC-MS). The analytical methods used for the characterisation of the cation-exchange resins and membrane include Fourier transform infrared coupled with attenuated total reflectance (FTIR-ATR), scanning electron microscopy attached to energy dispersive analyser (SEM/EDAX), Liquid nitrogen physisorption and nuclear magnetic resonance (NMR) respectively. A novel method was developed for carrying out esterification reaction in a gaseous phase system using a flat sheet polymeric membrane. Prior to the esterification reaction, different carrier gases were tested with ceramic membrane to determine the suitable carrier gases for the analysis of esterification product. The four carrier gases used for the permeation test were argon (Ar), helium (He), carbon dioxide (CO2) and nitrogen (N2). A 15nm pore size commercially available tubular ceramic support, consisting of 77%Al2O3 and 23%TiO2 with the porosity of 45% was used for the carrier gas investigation. The support was modified with silica based on the sol-gel dip-coating techniques. The dip-coated membrane exhibited a higher molar flux with He (0.046mol m-2s-1) and Ar (0.037mol m-2s-1) with a much lower flux for N2 (0.037mol m-2s-1) and CO2 (0.035 mol m-2s-1) at 0.30 bar. Helium gas with the highest permeation rate were identified as the suitable carrier gas for the analysis of esterification product with GC-MS. The esterification reaction in the presence of four cation-exchange resins to produce ethyl lactate was carried out between 60-160 oC in a batch and membrane processes to determine the effectiveness resin catalysts for LA esterification. The effect of external mass transfer diffusion limitation between the liquid components and the resin catalysts was avoided by increasing the agitation time of the esterification reaction. The percentage conversion rate of the lactic acid feed from the batch process esterification was found to be in the range of 98.6 to 99.8%. The reaction kinetics of the esterification reaction was described based on two simplified mechanisms of Langmuir Hinshelwood model to describe the adsorption components on the surface of the catalysts. The lactic acid feed gave a conversion rate of up to 100 % confirming the effectiveness of the acetate membrane impregnated resin catalysts in the selective removal of water for the separation of ethyl lactate. The significance of producing ethyl lactate through batch process intensified by a water-selective membrane processes can be recommended for industrial LA production.

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