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WO2018122700A1 - Procédé de production écologique de chitosane à partir d'acrididae, de tenebrionidae et gammaridae - Google Patents

Procédé de production écologique de chitosane à partir d'acrididae, de tenebrionidae et gammaridae Download PDF

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Publication number
WO2018122700A1
WO2018122700A1 PCT/IB2017/058279 IB2017058279W WO2018122700A1 WO 2018122700 A1 WO2018122700 A1 WO 2018122700A1 IB 2017058279 W IB2017058279 W IB 2017058279W WO 2018122700 A1 WO2018122700 A1 WO 2018122700A1
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WO
WIPO (PCT)
Prior art keywords
acrididae
gammaridae
tenebrionidae
chitosan
families
Prior art date
Application number
PCT/IB2017/058279
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English (en)
Inventor
Orhan ÖZCAN
İbrahim SERTDEMİR
Okşan KARAL YILMAZ
M. Naci YAZICIOĞLU
Original Assignee
Tubitak
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tubitak filed Critical Tubitak
Publication of WO2018122700A1 publication Critical patent/WO2018122700A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass

Definitions

  • the present invention relates to the production method of environmentally friendly chitosan.
  • the invention more particularly relates to the production method of chitosan which is environmentally friendly in terms of chemical factors and energy, from Acrididae (grashoppers), Tenebrionidae (darkling beetles, mealworms), and Gammaridae (Gammarus freshwater crustaceans) families, which are less likely to contain toxic or heavy metal compounds.
  • the thus obtained products principally include chitin and primary derivative thereof, chitosan.
  • Another biopolymer, chitosan has maintained its importance as a material of interest for the researchers especially in the last 50 years.
  • Chitosan which has many advantages when compared to chitin, is used in many industrial fields, primarily including food, cosmetics, agriculture, medicine, paper and textile industries. It has deemed necessary to develop various methods in order to obtain chitosan, whose area of use has expanded.
  • the Chinese Patent Application No. CN102037020 filed on 19.03.2008 within the state of the art discloses a method for producing chitosan from naturally occurring chitin-containing raw material, such as crustacean shells.
  • the products are first washed with a diluted hydrochloric acid mixture at a concentration of 3-4%. They are cleaned with water, and then aqueous sodium hydroxide at a concentration of 3 to 4% at 100°C is added for removing fat and protein, followed by washing the product again and drying.
  • aqueous sodium hydroxide at a concentration of 3 to 4% at 100°C is added for removing fat and protein, followed by washing the product again and drying.
  • chitin is placed at a 48% aqueous sodium hydroxide solution concentration and incubated for 6-8 hours. Afterwards, it is washed until neutralized. The resulting chitosan is dried.
  • demineralization is performed with 0.5N-0.1 N, i.e. 1.9-3.7 % HC1 in the method according to the invention and the used temperature is 50°C, not 100°C.
  • the deacetylation stage is performed with 48% NaOH for 6-8 hours at 100°C while in the method according to the invention, it is performed with 40% NaOH for 4 hours at 90°C.
  • heavy metal at PPM level is present here due to the use of sea-origin raw material, which is at PPB level in the method according to the invention. Further, the exemplified patent document does not mention depigmentation.
  • the Chinese Patent Application No. CN103665191A filed on 25.12.2013 within the state of the art discloses the production method of chitosan.
  • the shells are washed, dried, and then filtered. They are then soaked with hydrochloric acid. Afterwards, boiling with a sodium hydroxide solution, cooling and filtering are performed.
  • the protein removed shells are soaked with potassium permanganate. They are then subject to filtration, and subsequent to filtering the products, they are heated till complete decoloration. They are dried for forming chitin. Chitin is soaked with sodium hydroxide and cleaned. Once the hydroxide is removed, the product is dried and ground, thereby obtaining the chitosan.
  • KM11O 4 is used during deacetylation in the exemplified document and the use of said chemical is prohibited in Europe as well as in the USA. Moreover, the fact that the deacetylation occurs between 15-20 hours is associated with the used raw material. The harder chitin is, the longer the duration is.
  • the object of the present invention is to provide a production method of chitosan from Acrididae, Tenebrionidae and Gammaridae families.
  • Another object of the present invention is to provide an environmentally friendly chitosan production method with less energy and chemicals, using Acrididae, Tenebrionidae and Gammaridae families.
  • Another object of the present invention is to provide an environmentally friendly chitosan production method with low cost, using Acrididae, Tenebrionidae and Gammaridae families.
  • the method according to the invention is related to environmentally friendly chitosan production.
  • Dried organisms of Acrididae, Tenebrionidae and Gammaridae families are used as raw materials.
  • the method consists of seven main steps. The steps of the method are: making the organisms into powder form, pre-treating the powder in order to remove soluble organic and inorganic materials, removing lipids and soluble proteins, demineralization, deproteinization, and depigmentation and deacetylation for forming chitosan from chitin.
  • source organisms are selected from freshwater environment or edible insects.
  • the duration of depigmentation for obtaining an environmentally friendly, low-cost and high quality chitosan is shortened.
  • the invention is the production method of environmentally friendly chitosan from Acrididae, Tenebriomdae and Gammaridae families, wherein it comprises the steps of: making dead organisms of Acrididae, Tenebriomdae and Gammaridae families into powder form, boiling powdered organisms in water, removing lipids and soluble proteins, demineralization, deproteinization, depigmentation, deacetylation, and removing chitin in order to increase purity.
  • the organisms from Acrididae, Tenebriomdae and Gammaridae families, the chitin origin are made into powder form at 0.1-3 mm dimensions.
  • the powder is subject to pre-treatment so as to remove soluble organic and inorganic materials.
  • the chitin having been made into powder form is boiled with water for 1-4 hours (depending on the particle size) at 1-5 g powder/ 100 ml. After boiling, the organic phase with soluble substance content and the lipids accumulating on the water surface are removed.
  • the liquid in the aggregate that remains undissolved is removed as much as possible in order that it will not adversely affect the mineralization stage and that the used acid will be reduced.
  • deproteinization stage 5 g of demineralized insect waste is mixed with 100 ml of 2-5% NaOH for 2-4 hours at 50-70°C. After removing the liquid phase, the aggregate is first washed with 0.1N HC1 (0.1 Normality) and then with water. The base amount to be used is determined depending on the deproteinization temperature. First, longer deproteinization is useful for Acrididae family. Baseline base amount may be determined by measuring the pellet pH value with litmus paper.
  • decoloration step is also sufficient for depigmentation. In these cases, depigmentation steps can be omitted. It is not required to dry the pellet.
  • the decoloring solution is washed (50: EtOH 50: H 2 0 and 1 : H 2 0 2 ) in order to remove undissolved fraction pigments subsequent to the deproteinization step. Excessive H 2 0 2 is eliminated with water.
  • the use of lighter insects as raw material source means that H 2 0 2 is not required in the decoloring solution. Yellowish pinkish Gammaridae families do not require H 2 0 2 . It is because water and alcohol are not present when dried at 55°C. The darkening of the sample during the drying process results from excessive amount of H 2 0 2 or insufficient deproteinization. Therefore, the deproteinization step must be repeated.
  • the source organisms used here have a direct impact on the NaOH amount to be used. In case of a caterpillar pupa form, a more concentrated NaOH should be used.
  • Deacetylation is the step in which the chitin is turned into chitosan.
  • isolated chitin is dried.
  • 50 ml NaOH at 40% concentration is mixed for each g of chitin and incubated for 4 hours at 90°C (the temperature may be increased up to 150°C and thus the times period may be shortened).
  • the chitin/chitosan mixture is first washed with 0.1N HC1 (0.1 Normal HC1) and then with water.
  • the chitin/chitosan mixture is subject to 50°C for drying the same.
  • the dried mixture is mixed for 4-8 hours in the dark and dissolved in acetic acid.
  • the chitin-containing undissolved portion is removed.
  • the pH of the liquid portion is increased from pH 3-3.5 to pH 7.2-7.5 using 10% NaOH.
  • the chitin-chitosan mixture is made insoluble with this pH adjustment.
  • the liquid portion comprising chitosan is separated by physical methods, for example centrifuge or filtration. The remaining acetic acid is washed with water and removed.
  • lipids of Tenebrionidae family are edible, and thus they can be used not only in food but also in feed industry. The lipid content of such organisms can reach up to 30% of their weight.
  • the yield of the method is based on the source type. 100 g of the larval form of dried Tenebrio produces 25-35 g of edible oil. This oil can also be used as food additive for distilled alcoholic drinks such as tequila.
  • a 15-20 g of chitin/organic carbonate ash mixture is obtained for each 100 g of residue.
  • chitin is turned into chitosan
  • a mixture of 7 to 9 g containing chitosan, chitin and ash is obtained in the undissolved fraction.
  • the amount of ash varies between 15 and 20% of the mixture depending on the larval phase of the source. High yield chitin may be obtained in larvae molting period.
  • 100 g of the dried Acrididae yields in 30-35 g of locust leftovers which may be used as feed ingredient. 8.5 to 11 g of chitin-chitosan-ash mixture is obtained. The amount of chitosan varies between 2.5 and 4 g. During wing and late periods of adult Acrididae, high amounts of chitin/chitosan mixture is obtained.
  • chitin/ash per 100 g of dried organism is extracted after the deproteinization step.
  • the chitosan content in chitin-chitosan mixture is about 65%.
  • the solubility of acetic acid ensures that the final product weight of chitosan is as high as 84.6%.
  • Acrididae, Tenebrionidae and Gammaridae families can be produced at large amounts and they are commercially available.
  • the final product, chitosan is used in pharmaceutical, food and feed industries.
  • the by-products of the method are not toxic, which, in turn, makes such by-product suitable for use in feed and food industries.
  • the chemicals and materials used in this method are easy to obtain in bulk amounts.
  • the fact that only simple physical methods are utilized facilitates the method to be adjusted to large-scale fermenter systems.
  • the chemical agent amount and the total handling time is reduced; as a result, the production costs, time and required energy are also decreased. As a result, less waste material is produced reducing the cost of waste materials/wastes as well as the environmental problems.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne un procédé de production écologique de chitosane - à la fois en termes de contaminations chimiques et d'énergie - à partir d'Acrididae, de Tenebrionidae et Gammaridae, à savoir de familles qui sont moins susceptibles de contenir des composés métalliques toxiques ou lourds. Le procédé de production écologique de chitosane à partir d'Acrididae, de Tenebrionidae et Gammaridae selon l'invention est caractérisé en ce qu'il comprend les étapes de procédé suivantes : conversion d'organismes morts d'Acrididae, de Tenebrionidae et de Gammaridae sous une forme pulvérulente, prétraitement, élimination des lipides et des protéines solubles, déminéralisation, déprotéinisation, dépigmentation, désacétylation et séparation de la chitine pour augmenter la pureté.
PCT/IB2017/058279 2016-12-30 2017-12-21 Procédé de production écologique de chitosane à partir d'acrididae, de tenebrionidae et gammaridae WO2018122700A1 (fr)

Applications Claiming Priority (2)

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TRTR2016/20214 2016-12-30
TR201620214 2016-12-30

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WO2018122700A1 true WO2018122700A1 (fr) 2018-07-05

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112992276A (zh) * 2021-02-05 2021-06-18 滨州学院 不同水浴温度下鼠妇虫制备壳聚糖产率预测模型及方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991005808A1 (fr) * 1989-10-20 1991-05-02 Firextra Oy Procede de fabrication de chitosan et d'autres produits de carapaces d'organismes, notamment d'organismes marins
CA2201212A1 (fr) * 1996-03-27 1997-09-27 Gaston Picard Procede et appareil pour le recouvrement de la chitine
US6310188B1 (en) * 2000-01-24 2001-10-30 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Method for producing chitin or chitosan
US20140275507A1 (en) * 2013-03-15 2014-09-18 Johannes van Leeuwen Processes for isolating chitin and chitosan from fungal biomass

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991005808A1 (fr) * 1989-10-20 1991-05-02 Firextra Oy Procede de fabrication de chitosan et d'autres produits de carapaces d'organismes, notamment d'organismes marins
CA2201212A1 (fr) * 1996-03-27 1997-09-27 Gaston Picard Procede et appareil pour le recouvrement de la chitine
US6310188B1 (en) * 2000-01-24 2001-10-30 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Method for producing chitin or chitosan
US20140275507A1 (en) * 2013-03-15 2014-09-18 Johannes van Leeuwen Processes for isolating chitin and chitosan from fungal biomass

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ERDOGAN, S. ET AL.: "High similarity in physicochemical properties of chitin and chitosan from nymphs and adults of a grasshopper", INT. J. OF BIOL. MACROMOL., vol. 89, pages 118 - 126, XP029601571 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112992276A (zh) * 2021-02-05 2021-06-18 滨州学院 不同水浴温度下鼠妇虫制备壳聚糖产率预测模型及方法
CN112992276B (zh) * 2021-02-05 2022-10-18 滨州学院 不同水浴温度下鼠妇虫制备壳聚糖产率预测方法

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