RESUMO
During the past decades the understanding and prospects of enzyme-catalysed reactions have been massively widened and there are a number of implemented large-scale enzymatic processes mainly based in the use of commercial biocatalysts. As it might happen that the same process can be successfully carried out by different commercial lipases, the election of the biocatalyst must rely on productivity and economic considerations. This work presents productiveness and direct operation cost evaluation as a key tool for the selection between two commercial lipase catalysts, the versatile but expensive Novozym® 435 and a much more economical option, Lipozyme® TL IM, in the synthesis of spermaceti, a mixture of emollient esters with cosmetic applications. Proving that Novozym® 435 leads to minimum savings of 10% with respect to the cheapest immobilized derivative, biocatalyst cost does not appear to be the major contribution to the economics of the processes under study, due to their great capacity to be recovered and reused. At laboratory scale, the biggest economic investment is caused by substrates, which can be massively reduced at industrial scale by using bulk reagents. In such case, energy cost may be the major contribution to the process economy. This work proposes an optimized process ready to be scaled-up in order to accurately determine the energetic requirements of the possible industrial enzymatic synthesis.
Assuntos
Análise Custo-Benefício , Emolientes/química , Biocatálise , Ésteres/química , TemperaturaRESUMO
A solvent-free biocatalytic process for the synthesis of high quality cetyl laurate, myristate, palmitate and stearate has been optimized. This enzymatic procedure follows the fundamental principles of the Green Chemistry and lead to sustainable products, which can be labeled as natural and conform to the principal requirements for its use in high value-added goods. The four esters selected are the main components of spermaceti, a mixture of waxes very appreciated in cosmetic and pharmacy because of its physical properties and emolliency, which was formerly extracted from the head of the sperm whales. In this paper, the influence of the amount of biocatalyst, the commercially available Novozym(®) 435, and the temperature were studied in an open-air batch reactor before carrying out the synthesis in a high performance vacuum reactor with dry nitrogen input to shift the equilibrium towards product formation. Under optimal conditions, conversion was higher than 98.5 %. The characterization of the enzymatic cetyl esters puts in evidence that these are ultra-pure compounds, which have similar properties to the ones obtained through the conventional industrial processes with the extra benefit of being environmentally friendly.
Assuntos
Lipase/química , Palmitatos/síntese química , Enzimas Imobilizadas , Proteínas Fúngicas , Palmitatos/químicaRESUMO
BACKGROUND: Different strategies for the solvent-free enzymatic production of polyglycerol polyricinoleate (PGPR) were explored in an attempt to simplify and improve the process. Besides the conventional procedure (obtaining polyricinoleic acid, followed by its esterification with polyglycerol), two alternative methods are proposed: (1) reversing the synthesis order, i.e. esterification of polyglycerol with ricinoleic acid and then the condensation of ricinoleic acid with the previously obtained polyglycerol ester; and (2) the enzymatic synthesis of PGPR in a single-step process. RESULTS: The reaction sequences were carried out in an open-air reactor with free and immobilised lipases (triacylglycerol acylhydrolases, E.C. 3.1.1.3): Candida rugosa lipase to obtain polyricinoleic acid and Rhizopus oryzae lipase for the esterification of polyglycerol with the carboxyl group of ricinoleic or polyricinoleic acid. A co-immobilised derivative containing both lipases was used to catalyse the single-stage scheme. The three processes were carried out in a vacuum reactor, obtaining in every case PGPR that complied with the legal specifications of the European Community and recommendations provided in the Food Chemical Codex. CONCLUSION: The results demonstrate that all three protocols are viable for the enzymatic synthesis of PGPR and require similar reaction times. The single-stage scheme is easier to carry out.
Assuntos
Candida/enzimologia , Enzimas Imobilizadas/metabolismo , Glicerol/análogos & derivados , Lipase/metabolismo , Polímeros/metabolismo , Rhizopus/enzimologia , Ácidos Ricinoleicos/metabolismo , Biocatálise , Esterificação , Ésteres , Glicerol/metabolismoRESUMO
Esters are versatile compounds with a wide range of applications in various industries due to their unique properties and pleasant aromas. Conventionally, the manufacture of these compounds has relied on the chemical route. Nevertheless, this technique employs high temperatures and inorganic catalysts, resulting in undesired additional steps to purify the final product by removing solvent residues, which decreases environmental sustainability and energy efficiency. In accordance with the principles of "Green Chemistry" and the search for more environmentally friendly methods, a new alternative, the enzymatic route, has been introduced. This technique uses low temperatures and does not require the use of solvents, resulting in more environmentally friendly final products. Despite the large number of studies published on the biocatalytic synthesis of esters, little attention has been paid to the reactors used for it. Therefore, it is convenient to gather the scattered information regarding the type of reactor employed in these synthesis reactions, considering the industrial field in which the process is carried out. A comparison between the performance of the different reactor configurations will allow us to draw the appropriate conclusions regarding their suitability for each specific industrial application. This review addresses, for the first time, the above aspects, which will undoubtedly help with the correct industrial implementation of these processes.
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Esters from branched alcohols and dicarboxylic linear acids are widely used as lube bases due to their good performance at low temperatures. This work proposes a new process to synthesize bis(2-ethylbutyl) adipate and bis(2-ethylbutyl) sebacate by using the lipase-based catalyst Novozym® 435 in a solvent-free system. Different reaction strategies have been tested in order to minimize 2-ethyl-1-butanol losses due to its evaporation and optimum operation conditions have been determined: 2.5 % of biocatalyst, 50⯰C and a molar excess of alcohol of 15 % for the adipic diester and of 25 % for the sebacic one. It has also been proven that the immobilized enzyme can be reused in seven successive reaction cycles, achieving high yields without an appreciable reduction of activity. This biocatalytic pathway is a promising basis for the development of a more sustainable large scale process for obtaining biodegradable lubricants, as it is pointed out by productivity, economic and green metrics calculations.
Assuntos
Enzimas Imobilizadas , Lipase , Biocatálise , Enzimas Imobilizadas/metabolismo , Esterificação , Ésteres , Lipase/metabolismoRESUMO
Silicones are polymers that have properties of great interest for cosmetic and personal care industry, especially D4 (octamethylcyclotetrasiloxane) and D5 (decamethylcyclopentasiloxane), generically named cyclomethicones. However, different studies show the hypothesis that the use of these products is harmful and, therefore, several countries have adopted legislative actions to limit their use in personal care and cosmetic products. Faced with this new situation, different cosmetic companies began to look for different alternatives to cyclomethicones, mainly: organomodified silicones or esters. The former are based on the addition of functional groups to the main chain of silicon and oxygen. The latter represent a totally different line, since their functional group is the ester, but they have properties similar to silicones. Esters, especially branched-chain ones are currently the more promising alternative to replace cyclomethicones in cosmetic formulations. Nowadays, most of them are obtained by chemical reactions that require high temperatures and non-selective /contaminant catalysts that lead to low-quality final products. As an alternative, biocatalytic synthesis occurs always at mild operation conditions supplying ultra-pure, odor, and colorless products with less wastes and side reactions. Therefore, biocatalysis is a valid and environmentally sustainable option for the synthesis of silicone-substitute esters used in cosmetic formulations.