A method of producing chitosan

 

(57) Abstract:

The invention relates to a method of producing chitosan, which can be used as a sorbent, emulsifier, foaming agent. The method includes grinding the natural chitin-containing raw material extraction within 1-3 h of liquid carbon dioxide. Then carry out the first stage of decalcomania hydrochloric acid concentration of 0.8-2.5% at 5-10 times the volume of hydrochloric acid by weight of chitin-containing powder at a temperature of 35-50oC for 0.5 to 2 hours, washed with water and carry out the first stage of deproteinization enzyme in an amount of 0.1-0.5% of the dry weight of chitin-containing powder at pH 9,0-10,5 within 1-4 hours at a temperature of 50-70oWith and 4-7-fold excess of water, separated, washed out. Then conduct the second stage of decalcomania hydrochloric acid, washed with water and carry out a second phase of deproteinization enzyme. This is followed by a stage of deacetylation with sodium hydroxide, separating the chitosan from the mother liquor, rinse and drying. The invention allows to simplify the method of producing chitosan, reduce processing time, reduce the consumption of chemical materials and to obtain chitosan with high m the processing of natural materials, in particular to the processing of chitinous shells of crab and shrimp, dead bees with the production of chitosan, which can be used as a sorbent, emulsifier, foaming agent, etc.

The chitosans are polysaccharides derived from a polymer of vegetable origin - chitin. Chitosan, similarly gelatin, pectin, agar and agar belongs to the group of hydrocolloids.

Chitosan has anion-exchange properties, which opens wide possibilities of its use in ecology, medicine, cosmetics.

Chitosan is a biodegradable product, which is a big advantage compared to synthetic ion exchangers. To obtain chitosan mostly of chitin from crustacean shells and skeleton cuttlefish, insects, fungi, algae and others.

A method of obtaining chitosan, protected by the RF patent 2087483, class 08 In 37/08, 01 J 20/30, publ. 20.08.97. Chitosan is obtained by grinding natural chitin-containing raw material, calzinirovnie 1-2% solution of hydrochloric acid and deproteinization 1-5% sodium hydroxide solution, and washing and deacetylation 46-47% hydroxide solution nm each subsequent cycle of alternating stages is carried out at a higher temperature, than the previous one.

The disadvantage of this method is its multi-stage.

Closest to the claimed technical essence and the achieved result, selected as a prototype, is a method of producing chitosan, protected by the RF patent 2073017, class 08 In 37/08, 01 J 20/30, publ. 10.02.97.

The method includes grinding the natural chitin-containing raw material, decalcomania hydrochloric acid in a concentration of 1-5%, the deproteinization with the sodium hydroxide concentration of 1-5%, the deacetylation with sodium hydroxide, Department of chitosan from the mother liquor and drying. Before decalcomanias prepared aqueous suspension of powdered chitin-containing raw material at T:W=1:5 and handle raw materials sodium hydroxide to obtain the concentration in the suspension 1-4% at a temperature of 50-60oC for 1-3 h, decalcomania lead in two stages: the first stage of the process is conducted at a temperature of 25-30oAnd the concentration of hydrochloric acid 2-4% within 1-3 h, washed with water obtained solid phase at a temperature of 40-60oWith and carry out the second stage of decalcomania at a temperature of 30-35oAnd the concentration of hydrochloric acid 2-4% within 1-3 h, the deproteinization lead in two stages: at Teuku solid phase of water, before deacetylation tooth whitening solid phase hydrogen peroxide or sodium hypochlorite at a temperature of 40-60oC for 30 min, washed, conduct additional decalcomanie at a temperature of 20-35oC for 1-2 h with hydrochloric acid in a concentration of 2-4%, washed and dehydrated with sodium hydroxide concentration of 52% for 30 min, the deacetylation is carried out at a temperature of 80-90oC for 3 h with sodium hydroxide concentration of 52%.

The disadvantages of the method are its multi-stage, high durability, increased consumption of chemical materials, low molecular weight of the obtained chitosan.

Object of the present invention is an improved method of producing chitosan.

The technical result from the use of the invention is to simplify the method, reducing the duration, the production of chitosan with high molecular weight and reducing the consumption of chemical materials.

This result is achieved in that in the method of producing chitosan, including grinding of natural chitin-containing raw material extraction within 1-3 h with a subsequent stage of decalcomania the oxide of sodium, Department of chitosan from the mother liquor, washing and drying, extraction carried out with liquid carbon dioxide, after the first stage of decalcomania with flushing carried out the first stage of deproteinization enzyme in an amount of 0.1-0.5% of the dry weight of chitin-containing powder at pH 9,0-10,5 within 1-4 hours at a temperature of 50-70oWith and 4-7-fold excess of water, separated and washed chitin-containing powder, and then carry out the second stage of decalcomania and deproteinization enzyme. Stage decalcomania carried out with hydrochloric acid concentration of 0.8-2.5% at 5-10 times the volume of hydrochloric acid by weight of chitin-containing powder at a temperature of 35-50oC for 0.5-2 hours

A method of producing chitosan is as follows.

Natural chitin-containing raw materials (dried crumb crab shell or chainogo cover shrimp or dry dead bees) are ground to a fineness of 100-200 μm. Such ultrafine grinding of raw materials substantially accelerates the processes occurring during receipt of chitosan. The obtained chitin-containing powder is extracted with liquid carbon dioxide within 1-3 hours After extraction carried out the first stage decalin at a temperature of 35-50oC for 0.5 to 2 hours and Then the powder was washed with water at a temperature of 50-75oWith up to a pH of 5.4. After washing, carry out the first stage of deproteinization 4-7-fold volume of water at a pH of 9.0 to 10.5. The desired pH is achieved by adding sodium hydroxide. In the resulting suspension with stirring, add the enzyme, such as papain, Lipan, in an amount of 0.1-0.5% of the dry weight of chitin-containing powder. The resulting solution containing the peptides and amino acids, merge, and the chitin-containing powder is washed with water, followed by a second stage of decalcomania hydrochloric acid concentration of 0.8-2.5% in 5-7 times the amount by weight of dry chitin-containing powder at a temperature of 35-50oC for 0.5-2 hours After decalcomania the reaction mass is washed, then add 4-7-fold volume of water to the weight of dry chitin-containing powder, which increased by adding sodium hydroxide pH to 9.0-10.5 and add 0.1-0.5% enzyme by weight of dry chitin-containing powder. The deproteinization are within 2-4 hours at a temperature of 50-70oC. the resulting solution of peptides and amino acids is drained, add 2-4 volume of dry weight of chitin-containing powder 45-50% sodium hydroxide and spend the deacetylation of gpri a temperature of 60-80oWith up to pH 6.5 to 7.4, is separated in a centrifuge, dried and milled.

The extraction with liquid carbon dioxide simultaneously with the removal of lipids and part of the protein occurs and bleaching of raw materials. To reduce the molecular weight of the target product extraction is not affected. The use of the enzyme by deproteinization gives the possibility to reduce the molecular weight of chitosan. Alternating stages of decalcomania and deproteinization allows soft layers to remove the calcium and protein without destroying the chitin matrix.

The following examples explain the present invention.

Example 1.

The dried crumb crab shell is crushed in a mill to a fineness of 100-200 μm. The obtained chitin-containing powder is extracted with liquid carbon dioxide for 3 hours After extraction take 100 g of the obtained chitin-containing powder and conduct the first stage of decalcomania hydrochloric acid concentration of 2.5%, taken in a 5-fold amount by weight of chitin-containing powder (500 ml) for 0.5 h Then the powder was washed with water at a temperature of 75oWith up to a pH of 5.4. After washing, carry out the first stage of deproteinization 4-fold volume of water (232 ml) at pH of 10.5. Neobhodimosti papaya, for example LYPAINE 48000, production LYVEN, France, in the amount of 0.5% by weight of dry chitin-containing powder (0.29 grams). The first stage of deproteinization carried out for 2 h at 70oC. the resulting solution containing the peptides and amino acids, merge, and the chitin-containing powder is washed with water, followed by a second stage of decalcomania hydrochloric acid concentration of 2.5% in the 5-fold amount by weight of dry chitin-containing powder (246,5 ml) at a temperature of 35oC for 0.5 hours After decalcomania the reaction mass is washed, then add 4 times the amount of water by weight of dry chitin-containing powder (191,28 ml), which increased by adding sodium hydroxide pH to 10.5, and add 0,5% LYPAINE 48000 on the weight of dry chitin-containing powder (0.24 g). The deproteinization lead for 2 hours at a temperature of 70oC. the resulting solution of peptides and amino acids is drained, add 2 volume of dry weight of chitin-containing powder of 50% sodium hydroxide (92,78 ml) and spend the deacetylation with sodium hydroxide at a temperature of 95oC for 4 h

The obtained chitosan was washed with water at a temperature of 80oWith up to pH 7.4, is separated in a centrifuge, dried and milled.

Chitosan has trace the emer 2.

The dried crumb chainogo cover shrimp or dry dead bees are crushed in a mill to a fineness of 100-200 μm. The obtained chitin-containing powder is extracted with liquid carbon dioxide within 1 h After extraction takes 100 grams of chitin-containing powder and conduct the first stage of decalcomania hydrochloric acid concentration of 0.8%, taken in an amount 10 times the weight of chitin-containing powder (1000 ml) for 1 h and Then the powder was washed with water at a temperature of 50oWith up to a pH of 5.4. After washing, carry out the first stage of deproteinization 7-fold volume of water (406 ml) at pH of 9.0. The desired pH is achieved by adding sodium hydroxide. In the resulting suspension with stirring, add the enzyme, for example LYPAINE 48000, in an amount of 0.1% by weight of dry chitin-containing powder (0.06 g). The first stage of deproteinization carried out for 1 h at 50oC. the resulting solution containing the peptides and amino acids, merge, and the chitin-containing powder is washed with water, followed by a second stage of decalcomania hydrochloric acid concentration of 0.8% in 10-fold amount by weight of dry chitin-containing powder (493 ml) at a temperature of 50oC for 2 hours After decal the nd powder (334,6 ml), bringing by adding sodium hydroxide pH to 9.0, and add 0.1% papain (0,048 g) of dry weight of chitin-containing powder. The deproteinization lead for 2 hours at a temperature of 50oC. the resulting solution of peptides and amino acids is drained, add 4 volumes of dry weight of chitin-containing powder (185,2 ml of 45% sodium hydroxide and spend the deacetylation with sodium hydroxide at a temperature of 85oC for 2 h

The obtained chitosan was washed with water at a temperature of 60oWith up to pH 6.5, is separated in a centrifuge, dried and milled.

The obtained chitosan has the following characteristics: molecular weight - the 750,000 daltons, deacetylation 98%, ash content is 0.2.

Example 3.

Dry dead bees are crushed in a mill to a fineness of 100-200 μm. The obtained chitin-containing powder is extracted with liquid carbon dioxide within 2 hours After extraction takes 100 grams of chitin-containing powder and conduct the first stage of decalcomania hydrochloric acid concentration of 2.5%, taken in a 7-fold amount by weight of chitin-containing powder (700 ml) for 1 h and Then the powder was washed with water at a temperature of 75oWith up to a pH of 5.4. After washing exercise parvo is bauleni sodium hydroxide. In the resulting suspension with stirring papain, for example LYPAINE 48000, production LYVEN, France, in the amount of 0.5% by weight of dry chitin-containing powder (0.29 grams). The first stage of deproteinization carried out for 2 h at 50oC. the resulting solution containing the peptides and amino acids, merge, and the chitin-containing powder is washed with water, followed by a second stage of decalcomania hydrochloric acid concentration of 2.5% in 7-fold amount by weight of dry chitin-containing powder (to 344.4 ml) at a temperature of 40oC for 2 hours After decalcomania the reaction mass is washed, then add 5-fold volume of water to the weight of dry chitin-containing powder (238,5 ml), which increased by adding sodium hydroxide pH to 10.5, and add 0,5% LYPAINE 48000 on the weight of dry chitin-containing powder (0.24 g). The deproteinization lead for 2 hours at a temperature of 50oC. the resulting solution of peptides and amino acids is drained, add 3 volumes of dry weight of chitin-containing powder (138,9 ml) of 50% sodium hydroxide and spend the deacetylation with sodium hydroxide at a temperature of 95oC for 3 h

The obtained chitosan was washed with water at a temperature of 80oWith up to pH 7.4, separated on centlemen of deacetylation - 99%, ash content of 0.3%.

The molecular weight of the obtained chitosan determined by gel-chromatography, ash and deacetylation on THE 9289-001-57184729-01.

Extraction of chitin-containing raw material is less than 1 hour ineffective, and more than 3 h impractical due to the complete extract. With less than claimed, the amount of enzyme, pH, temperature and time on the stages of deproteinization protein is not completely washed away, and in their large values of the process and technologically impractical. The implementation of the method with excessive amounts of water and sodium hydroxide was determined experimentally and provides optimal conditions for the consumption of reagents and the reaction.

Thus, the proposed method allows to obtain chitosan with high molecular weight (prototype - to 100 kDa), with a high degree of deacetylation and low ash content, with good film-forming properties (elongation 600-650, prototype - 350-400). This reduces the number of stages, reduced processing time and consumption of chemical materials.

1. A method of producing chitosan, including grinding of natural chitin-containing raw material extraction in the tech what proteinsare, with intermediate washing with water, the deacetylation with sodium hydroxide, Department of chitosan from the mother liquor, washing and drying, characterized in that the extraction carried out with liquid carbon dioxide, after the first stage of decalcomania with flushing carried out the first stage of deproteinization enzyme in an amount of 0.1-0.5% of the dry weight of chitin-containing powder at pH 9,0-10,5 within 1-4 hours at a temperature of 50-70°C and 4-7-fold excess of water, separated and washed chitin-containing powder, and then carry out the second stage of decalcomania and deproteinization enzyme.

2. The method according to p. 1, characterized in that the stage of decalcomania carried out with hydrochloric acid concentration of 0.8-2.5% at 5-10 times the volume of hydrochloric acid by weight of chitin-containing powder at a temperature of 35-50°C for 0.5 to 2.0 hours

 

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