Abstract
New results are presented on a pilot and ecofriendly process to produce chitosan from waste shrimp shells. The process comprises demineralization with citric acid, enzymatic deproteinization with papain or bromelain to produce chitin and deacetylation to obtain chitosan (yield of 1 kg chitosan/kg shrimp shell, 64% deacetylated, 87.5% deproteinized and 98% demineralized). Shell particles of 1–25 mm were used instead of the shell powder that has been used in many studies. The developed process showed important technical and environmental advantages compared to the conventional process. A 10% increment in chitosan yield was obtained due a lower chitin hydrolysis. The ecofriendly process has 24% lower consumption of water. Residual water from citric acid demineralization does not need to be neutralized and can be re-circulated after the citrate salts recovery. Citrate salts are value-added byproducts for nutritional supplements and are easily recovered due to their low solubilities. Residual water from enzymatic deproteinization does not require neutralization and can be treated easier than water from the conventional process. Dissolved solids could be recovered by evaporation and used as animal feedstock for pink-colored fishes. The use of organic acids and enzymes in chitin extraction, compared to HCl and NaOH, does not require special materials for the reactors, reducing investment costs.
Highlights
• Ecofriendly process uses citric acid and enzymes instead of HCl and NaOH
• 10% increment in chitosan yield was obtained due a lower chitin hydrolysis
• Ecofriendly process has a 24% lower consumption of water
• Residual water does not need to be neutralized and can be re-used
• Citrate salts, proteins and carotenoids are value-added byproducts
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Data Availability
The datasets generated during and/or analyzed during the current study are available from the corresponding author on reasonable request.
References
Amado IR, González MP, Murado MA, Vázquez JA (2016) Shrimp wastewater as a source of astaxanthin and bioactive peptides. J Chem Technol Biotechnol 91:793–805. https://doi.org/10.1002/jctb.4647
Ameh AO, Abutu D, Isa MT, Rabiu U (2014a) Kinetics of demineralization of shrimp shell using lactic acid. Leonardo Electron J Pract Technol 24:13–22. http://lejpt.academicdirect.org/A24/013_022.pdf. Accessed 4 June 2022
Ameh AO, Isa MT, Abutu D, Danlami A (2014b) Kinetic modelling of the demineralization of shrimp exoskeleton using citric acid. Leonardo Electron J Pract Technol 13(25):99–108. http://lejpt.academicdirect.org/A25/099_108.pdf. Accessed 4 June 2022
Antunes-Valcareggi SA, Ferreira SRS, Hense H (2017) Enzymatic Hydrolysis of Blue Crab (Callinectes Sapidus) Waste Processing to Obtain Chitin, Protein, and Astaxanthin-Enriched Extract. 3(1):81–92. https://ijoear.com/issue-detail/issue-January-2017
Anwar M, Anggraeni AS (1823) Amin MH al (2017) Comparison of green method for chitin deacetylation. AIP Conf Proc 1:020071. https://doi.org/10.1063/1.4978144
AOAC (2005) Official Methods of Analysis of AOAC International 18th Edition, The Association of Official Analytical Chemists, Gaithersburg, MD, USA. Method 988.05. Ch. 4, p. 13
Arbia W, Arbia L, Adour L, Amrane A (2013) Chitin Extraction from Crustacean Shells Using Biological Methods - A review. Food Technol Biotechnol 51(1):12–25. https://hrcak.srce.hr/file/146860. Accessed 4 June 2022
Arvanitoyannis IS, Kassaveti A (2008) Fish industry waste: Treatments, environmental impacts, current and potential uses. Int J Food Sci Technol 43(4):726–745. https://doi.org/10.1111/j.1365-2621.2006.01513.x
Barnett M (2020) The Effects of Fish Processing Bio-waste on the Ocean’s Organisms and Nutrients. In: Sciencebuzz https://www.sciencebuzz.com/the-effects-of-fish-processing-bio-waste-on-the-oceans-organisms-and-nutrients/. Accessed 4 June 2022
Beddows CG, Ardeshir AG (1979) The production of soluble fish protein solution for use in fish sauce manufacture I. The use of added enzymes. Int J Food Sci Technol 14(6):603–612. https://doi.org/10.1111/j.1365-2621.1979.tb00907.x
Campana-Filho SP, Signini R (2002) Effects of additives and inert gas bubbling on the deacetylation of chitosan. Int J Polym Mater Polym Biomater 51(8):701–709. https://doi.org/10.1080/714975830
Chen H (2015) Lignocellulose biorefinery feedstock engineering. Lignocellulose Biorefinery Engineering, 1st edn. Woodhead Publishing, Sawston, pp 37–86
Czechowska-Biskup R, Jarosińska D, Rokita B, Ulański P, Rosiak J (2012) Determination of degree of deacetylation of chitosan - Comparision of methods. Progress on Chemistry and Application of Chitin and its Derivatives 17:5–20. https://www.researchgate.net/publication/288104933_Determination_of_degree_of_deacetylation_of_chitosan_-_Comparision_of_methods. Accessed 4 June 2022
Dai Y, van Spronsen J, Witkamp GJ, Verpoorte R, Choi YH (2013) Ionic liquids and deep eutectic solvents in natural products research: Mixtures of solids as extraction solvents. J Nat Prod 76(11):2162–2173. https://doi.org/10.1021/np400051w
Dalei J, Sahoo D (2015) Extraction and characterization of astaxanthin from the crustacean shell waste from shrimp processing. Int J Pharm Sci Res IJPSR 6:2532–2537. https://doi.org/10.13040/IJPSR.0975-8232.6(6).2532-37
de Andrade SMB, Ladchumananandasivam R, da Rocha BG, da Belarmino D, Galvao A (2012) The Use of Exoskeletons of Shrimp (Litopenaeus vanammei) and Crab (Ucides cordatus) for the Extraction of Chitosan and Production of Nanomembrane. Mater Sci Appl 3:495–508. https://doi.org/10.4236/msa.2012.37070
de Lencastre Novaes LC, Jozala AF, Lopes AM, Santos VC, Gava P, Pessoa A (2016) Stability, purification, and applications of bromelain: A review. Biotechnol Prog 32(1):5–13. https://doi.org/10.1002/btpr.2190
di Nardo T, Hadad C, Nguyen Van Nhien A, Moores A (2019) Synthesis of high molecular weight chitosan from chitin by mechanochemistry and aging. Green Chem 21:3276–3285. https://doi.org/10.1039/c9gc00304e
Duan B, Gao H, He M, Zhang L (2014) Hydrophobic modification on surface of chitin sponges for highly effective separation of oil. ACS Appl Mater Interfaces 6(22):19933–19942. https://doi.org/10.1021/am505414y
Dudhgara PR, Sunil B, Anjana G (2015) Hide dehairing and laundry detergent compatibility testing of thermostable and solvents tolerant alkaline protease from hot spring isolate bacillus cohniiU3. OnLine J Biol Sci 15(3):152–161. https://doi.org/10.3844/ojbsci.2015.152.161
El-banna FS, Mahfouz ME, Leporatti S, El-kemary M, Hanafy N (2019) Chitosan as a natural copolymer with unique properties for the development of hydrogels. Appl Sci (Switzerland) 9(11):2193. https://doi.org/10.3390/app9112193
Ferreira JF, Santana JCC, Tambourgi EB (2011) The effect of pH on bromelain partition from Ananas comosus by PEG4000/Phosphate ATPS. Braz Arch Biol Technol 54(1):125–132. https://doi.org/10.1590/S1516-89132011000100017
Fu X, Zhu L, Li L, Zhang T, Li M, Mou H (2019) Eco-friendly preparation of chitooligosaccharides with different degrees of deacetylation from shrimp shell waste and their effects on the germination of wheat seeds. Marine Life Sci Technol 1:95–103. https://doi.org/10.1007/s42995-019-00012-3
Gagné N, Simpson BK (1993) Use of Proteolytic Enzymes to Facilitate the Recovery of Chitin from Shrimp Wastes. Food Biotechnol 7(3):253–263. https://doi.org/10.1080/08905439309549861
Gbenebor OP, Adeosun SO, Lawal GI (2017) Acetylation, crystalline and morphological properties of structural polysaccharide from shrimp exoskeleton. Eng Sci Technol Int J 20(3):1155–1165. https://doi.org/10.1016/j.jestch.2017.05.002
Gómez-Rico MF, Font R, Fullana A, Martín-Gullón I (2005) Thermogravimetric study of different sewage sludges and their relationship with the nitrogen content. J Anal Appl Pyrol 74(1–2):421–428. https://doi.org/10.1016/j.jaap.2004.11.029
Gómez-Ríos D, Barrera-Zapata R, Ríos-Estepa R (2017) Comparison of process technologies for chitosan production from shrimp shell waste: A techno-economic approach using Aspen Plus ®. Food Bioprod Process 103:49–57. https://doi.org/10.1016/j.fbp.2017.02.010
Gopakumar DA, Pai AR, Pasquini D, Leu S, Thomas S (2018) Nanomaterials-State of Art, New Challenges, and Opportunities. Nanoscale Materials in Water Purification, 1st edn. Elsevier, Amsterdam, pp 1–24
Gyawali D, Nair P, Zhang Y, Tran R, Zhang C, Samchukov M, Makarov M, Kim H, Yang J (2010) Citric acid-derived in situ crosslinkable biodegradable polymers for cell delivery. Biomaterials 31(34):9092–9105. https://doi.org/10.1016/j.biomaterials.2010.08.022
Hamed I, Özogul F, Regenstein JM (2016) Industrial applications of crustacean by-products (chitin, chitosan, and chitooligosaccharides): A review. Trends Food Sci Technol 48:40–50. https://doi.org/10.1016/j.tifs.2015.11.007
Hongkulsup C, Khutoryanskiy V, v., Niranjan K, (2016) Enzyme assisted extraction of chitin from shrimp shells (Litopenaeus vannamei). J Chem Technol Biotechnol 91(5):1250–1256. https://doi.org/10.1002/jctb.4714
Hossain MS, Iqbal A (2014) Production and characterization of chitosan from shrimp waste. J Bangladesh Agril Univ 12(1):153–160. https://doi.org/10.3329/jbau.v12i1.21405
Hu J, Lu W, Lv M, Wang Y, Ding R, Wang L (2019) Extraction and purification of astaxanthin from shrimp shells and the effects of different treatments on its content. Braz J Pharmacogn 29(1):24–29. https://doi.org/10.1016/j.bjp.2018.11.004
Hu X, Tian Z, Li X, Wang S, Pei H, Sun H, Zhang Z (2020) Green, Simple, and Effective Process for the Comprehensive Utilization of Shrimp Shell Waste. ACS Omega 5(30):19227–19235. https://doi.org/10.1021/acsomega.0c02705
Hülsey MJ (2018) Shell biorefinery: A comprehensive introduction. Green Energy Environ 3(4):318–327. https://doi.org/10.1016/j.gee.2018.07.007
Ibrahim HM, Salama MF, El-Banna HA (1999) Shrimp’s waste: Chemical composition, nutritional value and utilization. Nahrung – Food 43(6):418–423. https://doi.org/10.1002/(sici)1521-3803(19991201)43:6<418::aid-food418>3.0.co;2-6
Ismael MNM, el Nemr A, el Ashry ESH, Abdel Hamid H (2020) Removal of Hexavalent Chromium by Cross-Linking Chitosan and N, N’-Methylene Bis-Acrylamide. Environ Process 7:911–930. https://doi.org/10.1007/s40710-020-00447-2
Jeuniaux C, Compère P, Goffinet G (1986) Structure, synthèse et dégradation des chitinoprotéines de la cuticule des crustacés décapodes. Ital J Zool 53:183–196. https://doi.org/10.1080/11250008609355502
Ju X, Grego C, Zhang X (2013) Specific effects of fiber size and fiber swelling on biomass substrate surface area and enzymatic digestibility. Biores Technol 144:232–239. https://doi.org/10.1016/j.biortech.2013.06.100
Kaya M, Lelešius E, Nagrockaite R, Sargin I, Arslan G, Mol A, Baran T, Can E, Bitim B (2015) Differentiations of Chitin content and surface morphologies of chitins extracted from male and female grasshopper species. PLoS ONE 10(1):e0115531. https://doi.org/10.1371/journal.pone.0115531
Ketnawa S, Chaiwut P, Rawdkuen S (2011) Aqueous two-phase extraction of bromelain from pineapple peels (“Phu Lae” cultv.) and its biochemical properties. Food Sci Biotechnol 20(5):1219–1226. https://doi.org/10.1007/s10068-011-0168-5
Kim WJ, Lee WG, Theodore K, Chang HN (2001) Optimization of culture conditions and continuous production or chitosan by the fungi, Absidia Coerulea. Biotechnol Bioprocess Eng 6(1):6–10. https://doi.org/10.1007/BF02942243
Liang Z, Wang Q, Dong B, Jiang B, Xing F (2018) Ion-triggered calcium hydroxide microcapsules for enhanced corrosion resistance of steel bars. RSC Adv 69(8):39536–39544. https://doi.org/10.1039/c8ra07382a
Lynch JM, Barbano DM (1999) Kjeldahl nitrogen analysis as a reference method for protein determination in dairy products. J AOAC Int 82(6):1389–1398. https://doi.org/10.1093/jaoac/82.6.1389
Maddaloni M, Vassalini I, Alessandri I (2020) Green Routes for the Development of Chitin/Chitosan Sustainable Hydrogels. Sustain Chem 1(3):325–344. https://doi.org/10.3390/suschem1030022
Mahmoud NS, Ghaly AE, Arab F (2007) Unconventional approach for demineralization of deproteinized crustacean shells for chitin production. Am J Biochem Biotechnol 3(1):1–9. https://doi.org/10.3844/ajbbsp.2007.1.9
Mandeville S, Yaylayan V, Simpson BK (1992) Proximate analysis, isolation and identification of amino acids and sugars from raw and cooked commercial shrimp waste. Food Biotechnol 6(1):51–64. https://doi.org/10.1080/08905439209549821
Martínez Ruano JA, Taimbu de la Cruz CA, Orrego Alzate CE, Cardona Alzate CA (2019) Techno–Economic Analysis of Chitosan-Based Hydrogels Production. In: Mondal, M. (eds) Cellulose-Based Superabsorbent Hydrogels. Polymers and Polymeric Composites: A Reference Series, 1st edn. Springer, Cham, pp 1769–1790
Minh TLT, Truc TT, Osako K (2022) The effect of deproteinization methods on the properties of glucosamine hydrochloride from shells of white leg shrimp (Litopenaeus vannamei) and black tiger shrimp (Penaeus monodon). Ciência Rural 52(1):1–6. https://doi.org/10.1590/0103-8478cr20200723
Morrow JC (2002) Biotechnological utilization of Nephrops shell waste. Faculty of veterinary medicine. Dissertation, University of Glasgow
National Center for Biotechnology Information (2022a) Citric acid. In: PubChem Compound Summary for CID 311. https://pubchem.ncbi.nlm.nih.gov/compound/Citric-acid. Accessed 2 Mar 2022a
National Center for Biotechnology Information (2022b) Calcium citrate. In: PubChem Compound Summary for CID 13136. https://pubchem.ncbi.nlm.nih.gov/compound/Calcium-citrate. Accessed 2 Mar 2022b
No HK, Cho YI, Kim HR, Meyers SP (2000) Effective deacetylation of chitin under conditions of 15 psi/121 °C. J Agric Food Chem 48(6):2625–2627. https://doi.org/10.1021/jf990842l
No H, Lee M (1995) Isolation of chitin from crab shell waste. J Korean Soc Food Nutr 24(1):105–103. https://agris.fao.org/agris-search/search.do?recordID=KR9503117. Accessed 2 Mar 2022
Noordman TR, Ketelaar TH, Donkers F, Wesselingh JA (2002) Concentration and desalination of protein solutions by ultrafiltration. Chem Eng Sci 57(4):693–703. https://doi.org/10.1016/S0009-2509(01)00403-1
Patria A (2013) Production and characterization of Chitosan from shrimp shells waste. AACL Bioflux 6(4):339–334. http://www.bioflux.com.ro/aacl. Accessed 2 Mar 2022
Paulino AT, Simionato JI, Garcia JC, Nozaki J (2006) Characterization of chitosan and chitin produced from silkworm crysalides. Carbohyd Polym 64(1):98–103. https://doi.org/10.1016/j.carbpol.2005.10.032
Pavan R, Jain S, Shraddha KA (2012) Properties and Therapeutic Application of Bromelain: A Review. Biotechnol Res Int 2012:976203. https://doi.org/10.1155/2012/976203
Percot A, Viton C, Domard A (2003) Characterization of shrimp shell deproteinization. Biomacromol 4(5):13–80. https://doi.org/10.1021/bm034115h
Phillips AT, Signs MW (2004) Desalting, Concentration, and Buffer Exchange by Dialysis and Ultrafiltration. Curr Protoc Protein Sci Ch4:4. https://doi.org/10.1002/0471140864.ps0404s38
Pires CTGVMT, Vilela JAP, Airoldi C (2014) The effect of chitin alkaline deacetylation at different condition on particle properties. Proc Chem 9:220–225. https://doi.org/10.1016/j.proche.2014.05.026
Quan C, Turner C (2009) Extraction of astaxanthin from shrimp waste using pressurized hot ethanol. Chromatographia 70(1–2):247–251. https://doi.org/10.1365/s10337-009-1113-0
Queiroz MF, Melo KRT, Sabry DA, Sassaki GL, Rocha HAO (2015) Does the use of chitosan contribute to oxalate kidney stone formation? Mar Drugs 13(1):141–158. https://doi.org/10.3390/md13010141
Rahman MM, Khosravi S, Chang KH, Lee SM (2016) Effects of dietary inclusion of astaxanthin on growth, muscle pigmentation and antioxidant capacity of juvenile rainbow trout (Oncorhynchus mykiss). Prev Nutr Food Sci 21(3):281–288. https://doi.org/10.3746/pnf.2016.21.3.281
Ravi Kumar MNV (2000) A review of chitin and chitosan applications. React Funct Polym 46(1):1–27
Roer R, Dillaman R (1984) The structure and calcification of the crustacean cuticle. Integr Comp Biol 24(4):893–909. https://doi.org/10.1093/icb/24.4.893
de Ros DGL, Cerro MTL, Canovas ER, Turk OD, de Yerba J, Roca J (2017) Chitin and chitosan producing methods. European Patent Office EP3034612A1. https://patents.google.com/patent/EP3034612A1/en. Accessed 4 June 2022
Sakhaee K, Bhuket T, Adams-Huet B, Sudhaker Rao D (1999) Meta-analysis of calcium bioavailability: A comparison of calcium citrate with calcium carbonate. Am J Ther 6(6):313–322. https://doi.org/10.1097/00045391-199911000-00005
Salih SS, Ghosh TK (2018) Preparation and Characterization of Chitosan-Coated Diatomaceous Earth for Hexavalent Chromium Removal. Environ Process 5(2018):23–29. https://doi.org/10.1007/s40710-017-0280-5
Setyahadi S, Hermansyah H, Aruan JB (2014) Chitin Extraction Fermentation Penaeus vannamei Shell Wastes with High Density Cell by Recycle Culture Cells. J Chitin Chitosan Sci 2(3):209–2015. https://doi.org/10.1166/jcc.2014.1061
Shen X, Shamshina JL, Berton P, Bandomir J, Wang H, Gurau G, Rogers R (2016) Comparison of Hydrogels Prepared with Ionic-Liquid-Isolated vs Commercial Chitin and Cellulose. ACS Sustain Chem Eng 4(2):471–480. https://doi.org/10.1021/acssuschemeng.5b01400
Shishov A, Bulatov A, Locatelli M, Carradori S, Andruch V (2017) Application of deep eutectic solvents in analytical chemistry. A Review. Microchem J 135:33–38. https://doi.org/10.1016/j.microc.2017.07.015
Soils Matter (2021) “Macronutrients” versus “micronutrients”? https://soilsmatter.wordpress.com/2014/07/11/macronutrients-versus-micronutrients/. Accessed 24 Aug 2021
Soon CY, Tee YB, Tan CH, Rosnita AT, Khalina A (2018) Extraction and physicochemical characterization of chitin and chitosan from Zophobas morio larvae in varying sodium hydroxide concentration. Int J Biol Macromol 108:135–142. https://doi.org/10.1016/j.ijbiomac.2017.11.138
Ssekatawa K, Byarugaba DK, Wampande EM, Moja TN, Nxumalo E, Maaza M, Sackey J, Ejobi F, Kirabira JB (2021) Isolation and characterization of chitosan from Ugandan edible mushrooms, Nile perch scales and banana weevils for biomedical applications. Sci Rep 11:4116. https://doi.org/10.1038/s41598-021-81880-7
Steine G, Alfnes F, Rørå MB (2005) The effect of color on consumer WTP for farmed salmon. Mar Resour Econ 20(2):211–219. https://doi.org/10.1086/mre.20.2.42629470
Synowiecki J, Al-Khateeb NAAQ (2000) The recovery of protein hydrolysate during enzymatic isolation of chitin from shrimp Crangon crangon processing discards. Food Chem 68(2):147–152. https://doi.org/10.1016/S0308-8146(99)00165-X
Tolesa LD, Gupta BS, Lee MJ (2019) Chitin and chitosan production from shrimp shells using ammonium-based ionic liquids. Int J Biol Macromol 130:818–826. https://doi.org/10.1016/j.ijbiomac.2019.03.018
Valdez-Peña AU, Espinoza-Perez JD, Sandoval-Fabian GC, Balagurusamy N, Henandez-Rivera A, De-la-Garza-Rodriguez I, Contreras-Esquivel J (2010) Screening of industrial enzymes for deproteinization of shrimp head for chitin recovery. Food Sci Biotechnol 19:553–557. https://doi.org/10.1007/s10068-010-0077-z
Wang WP, Du YM, Wang XY (2008) Physical properties of fungal chitosan. World J Microbiol Biotechnol 24:2717–2720. https://doi.org/10.1007/s11274-008-9755-x
Wang X, Tang R, Zhang Y, Yu Z, Qi C (2016) Preparation of a novel chitosan-based biopolymer dye and application in wood dyeing. Polymers (basel) 8(9):38. https://doi.org/10.3390/polym8090338
Womac AR, Igathinathane C, Bitra P, Miu P, Yang T, Sokhansanj S, Narayan S (2007) Biomass pre-processing size reduction with instrumented mills. In: 2007 ASABE Annual International Meeting, Technical Papers
Yeh AI, Huang YC, Chen SH (2010) Effect of particle size on the rate of enzymatic hydrolysis of cellulose. Carbohyd Polym 79(1):192–199. https://doi.org/10.1016/j.carbpol.2009.07.049
Younes I, Ghorbel-Bellaaj O, Nasri R, Chaabouni M, Rinaudo M, Nasri M (2012) Chitin and chitosan preparation from shrimp shells using optimized enzymatic deproteinization. Process Biochem 47(12):2032–2039. https://doi.org/10.1016/j.procbio.2012.07.017
Yu G, Liu H, Venkateshan K, Yan S, Cheng J, Sun X, Wang D (2011) Functional, physiochemical, and rheological properties of duckweed (SPIRODELA POLYRHIZA) protein. Trans ASABE 54(2):555–561. https://doi.org/10.13031/2013.36459
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The authors gratefully acknowledge the financial support provided by “Ministerio de Ciencia Tecnología e Innovación – MINCIENCIAS – Colombia” and “Gobernación de Nariño (Colombia)” through Contract 80740-225-2019 (CONVOCATORIA I+D+i NARIÑO 818-2018).
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This work was supported by “CONVOCATORIA I + D + i NARIÑO 818–2018”, Contract 80740–225-2019.
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Pérez, W.A., Marín, J.A., López, J.N. et al. Development of a Pilot-ecofriendly Process for Chitosan Production from Waste Shrimp Shells. Environ. Process. 9, 55 (2022). https://doi.org/10.1007/s40710-022-00605-8
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DOI: https://doi.org/10.1007/s40710-022-00605-8