Pink shrimp (P. brasiliensis and P. paulensis) residue: Supercritical fluid extraction of carotenoid fraction

https://doi.org/10.1016/j.supflu.2012.11.020Get rights and content

Abstract

The objective of this work was to study the technical and the economical viability to concentrate the carotenoid components by means of supercritical fluid extraction (SFE) from pink shrimp processing waste. The raw material was pretreated using heat treatment, milling and drying. The SFE with carbon dioxide (CO2) was evaluated by varying the raw material moisture content, the solvent flow rate, the conditions of temperature and pressure and the use co-solvent (hexane + isopropanol solution, 50:50, and sunflower oil) at concentrations of 2 and 5%. SFE curves were modeled using well-known mathematical models from literature, and mass transfer coefficients were determined and validated through correlations with dimensionless numbers. The process cost for industrial application was also estimated. The extracts were evaluated in terms total carotenoid content, carotenoid profile, astaxanthin yield and UV–Vis scanning spectrometry. The results indicated that shrimp waste can be used for concentrating natural carotenoids. The SFE was favorable at 13.3 g/min of CO2 flow rate and at 11.210% of raw material moisture content. The Sovová [21] model best fitted in the experimental data and indicated higher influence of convection when compared to diffusion. In addition, the results from the dimensionless number correlations indicated that forced convection is more important than natural convection. The carotenoid extraction increases with enhancing the CO2 density. The highest astaxanthin yield was obtained by CO2 at 300 bar/333.15 K. The cost analysis suggested the application of a SFE unit with 2 × 400 L vessels for 25 min extraction, to treat the pink shrimp residue, as the most lucrative process design.

Highlights

► Experimental curves were better adjusted in Sovová’s model. ► SFE from pink shrimp has higher influence of convection when compared to diffusion. ► Forced convection was more important than natural convection in the SFE process. ► Shrimp residue is an important raw material to obtain high content of astaxanthin. ► SFE in the CER period, using 2 × 400 L unit, presented a low specific cost.

Introduction

According to the Food and Agriculture Organization of the United Nations [1], the worldwide capture of marine fishes was 78.9 million ton in 2011, with 3.8 percent consisted of marine crustaceans. World aquaculture production of crustaceans in 2010 consisted of freshwater species (29.4 percent) and marine species (70.6 percent). The production of marine species is dominated by white leg shrimp (Penaeus vannamei), including substantial production in freshwater. In sharp contrast, the giant tiger prawn has lost importance in the last decade. Major freshwater species include red swamp crayfish, Chinese mitten crab, oriental shrimp and giant river prawn. In South America it has shown strong and continuous growth, particularly in Brazil and Peru. In terms of volume, aquaculture in North and South America is dominated by finfishes (57.9 percent), crustaceans (21.7 percent) and molluscs (20.4 percent) [1]. Particularly in the State of Santa Catarina (Brazil), the crustacean production increased 39% in 2007 compared to 2006 [2].

Processed shrimps can be classified as headless shrimp and peeled shrimp, generating the just the head, the cephalothorax, and/or the exoskeleton as the processing residue(s). The cephalothorax consists of 35–45% of raw material and the exoskeleton around 47%. Together they represent up to 70% (w/w) of the raw material [3]. This waste is composed primarily of cephalothorax, exoskeleton, viscera and muscle remnants, and contributes to increase pollution when improperly disposed [4].

The processing of the shrimp waste represents an alternative to valorize an industrial residue, mainly because this material can be considered a source of substances used as food ingredients and other applications. Besides the above mentioned economic aspect, the environmental feature is also relevant. A very valuable by-product that can be recovered from the shrimp residue is the enriched carotenoid fraction because of its highly potential demand for food and pharmaceutical industries [5], [6].

The recovery of valuable components from an industrial residue can be achieved by means of extraction methods and also, the technique selected for the extraction is of decisive importance for the product quality. There are several conventional procedures for the carotenoid extraction from a natural raw material such as maceration [6], [7], [8], Soxhlet [6], ultrasound [6], [9], [10], and oil extraction [6], [8], [11] techniques. Each method presents advantages and disadvantages and the effectiveness of each method depends on the product application and quality. The limitations of conventional processes are: high energy costs; elevated solvent use and time consuming; high temperatures, affecting the thermo labile substances; low selectivity; and retention of solvent traces in the solute [12], [13].

An alternative to conventional techniques for the extraction of the carotenoid components fraction from shrimp residue is the supercritical technology by means of carbon dioxide (CO2) [14]. Supercritical fluid extraction (SFE) has numerous advantages over conventional techniques such as the use of low temperatures and reduced energy consumption, efficiency in solvent use with recycling possibility, prevention of oxidation reactions and high product quality due to the absence of solvent in solute phase, it is a flexible process due to possibility of continuous adjustment of the solubility and selectivity power of the solvent through the selection of processing parameters [15], [16].

In spite of the well known advantages of the process such as high quality product, SFE has an economical constraint due to the high investment cost inherent to high pressure processes [17]. The cost of manufacturing (COM) is influenced by factors that can be divided into three categories: direct costs, fixed costs, and general expenses. Direct costs take into account expenses that depend directly on the production rate, such as raw material, utilities, and operating labor. Fixed cost does not depend directly on the production rate and must be considered even if the operation is interrupted. Examples of items included in this cost are equipment depreciation, taxes and insurance. General expenses are the items necessary to maintain the business and consist of administrative cost, sales expenses, research and development, among others [18], [19], [20].

The study of supercritical extraction curves and the knowledge of the effects of the operational variables allow the definition of the extractor volume and solvent flow rate (QCO2). According to the literature, the overall extraction curves are clearly divided into three periods [21], [22], [23] controlled by different mass transfer mechanisms: (a) the constant extraction rate (CER) period, where the convection is the dominant mass transfer mechanism; (b) the falling extraction rate (FER) period, where the diffusion mechanism starts, operating combined with convection; (c) the diffusion-controlled period, where the mass transfer occurs manly by diffusion in the bed and inside the solid substratum particles. The main objective of the modeling of overall extraction curves is to define parameters for process design, such as equipment dimensions, solvent flow rate and particle size. These parameters are used to predict curves in order to estimate the process viability in industrial scale [17]. Several mathematical models are presented in the literature to describe the SFE. A model should be a mathematical instrument which reflects the physical behavior of the solid structure and experimental observations [23]. Then, it can be used as a simulation tool for SFE curves on the industrial application of supercritical technology.

Otherwise, mathematical models that represent real mass transfer phenomena contain two kinds of uncertainties: (a) model uncertainty, due to a non-exact physical–mathematical description of the system, for instance an oversimplification; (b) parameter uncertainty, resulting from errors from the experimental data employed to estimate the model parameters [24]. In addition, some of the important process parameters can be enlisted, such as the mean value of the particle diameter (grounded raw material), the solute diffusivity in the supercritical fluid, the solid mass transfer coefficient (inside the particles), among others. These properties are determined from the experimental results considering a certain degree of inaccuracy: even if the mathematical model is correct from a physical–mathematical point of view, uncertainty in parameters can affect the model predictions.

Considering the cited literature information, this work aimed to evaluate the SFE efficiency in order to concentrate carotenoids from the pink shrimp (Penaeus brasiliensis and Penaeus paulensis) processing waste. The process efficiency was studied by the effect of the operational conditions and co-solvents used for the extraction on solute characterization, analyzed by determining the carotenoidic and the UV–Visible spectral profiles. The kinetics and modeling of SFE curves were also determined, and the adjustable parameters were evaluated using as dimensionless number correlation. Finally, the process costs were estimated.

Section snippets

Sample preparation

The raw material consists of pink shrimp (P. brasiliensis and P. paulensis) processing waste, composed essentially by head, carapace, and tail. The residue was provided by Peixaria Nelson Santos (Florianópolis, Santa Catarina, southern Brazil), sited at the local public market. The residue from the shrimp processing was supplied as one single sample, representative from the high season production in May, 2010 and belong to same family and genus, differing only in the species according to their

Kinetics and modeling of SFE from pink shrimp residue

The three experimental and modeled extraction curves obtained from assays group (a), conducted at 200 bar, 333.15 K and at: (1) 46.30 ± 0.06% moisture content and 8.3 g CO2/min; (2) 46.30 ± 0.06% moisture content and 13.3 g CO2/min; (3) 11.210 ± 0.005% moisture content and 13.3 g CO2/min; are presented in Fig. 1. The kinetic results from the extraction curves and the modeling parameters obtained for the SFE from pink shrimp residue, evaluating CO2 flow rate (8.3 and 13.3 g/min) and raw material moisture

Conclusions

The kinetic study of SFE from pink shrimp processing residue as function of the moisture content of raw material and CO2 flow rate variables indicates that these parameters affected the process mass transfer rate, the CER period and the global yield. The modeling of SFE from shrimp residue showed the best adjustments achieved by Sovová’s, although good results were also obtained by the logistic and SSP models. However, only Sovová’s model supplies information about different mass transfer

Acknowledgements

The authors wish to thank Capes for the doctoral fellowship, and CNPq (470862/2010-6) for the finantial support and Peixaria Nelson Santos for the raw material supply.

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