CA2067788A1 - Method for manufacture of chitosan and other products from shells of organisms, especially marine organisms - Google Patents
Method for manufacture of chitosan and other products from shells of organisms, especially marine organismsInfo
- Publication number
- CA2067788A1 CA2067788A1 CA002067788A CA2067788A CA2067788A1 CA 2067788 A1 CA2067788 A1 CA 2067788A1 CA 002067788 A CA002067788 A CA 002067788A CA 2067788 A CA2067788 A CA 2067788A CA 2067788 A1 CA2067788 A1 CA 2067788A1
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- Prior art keywords
- shells
- organisms
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- solutions
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-
- 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
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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)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a method of manufacture of chitosan and other products, such as chitin and proteins, from the shells of organisms, especially marine organisms, as a result of the reaction stages of deproteinization by alkaline solutions, demineralization by acidic solutions and deacetylation by concentrated alkaline solutions. The method comprises at least two successive stages of said three stages. The chitosan is manufactured so that in the shells of organisms, especially marine organisms, such as crabs or shrimps, are placed in a space in a reactor limited by a wall pervious to reaction liquids but retaining said shells of organisms. Thereafter they are subjected to a continuous action of reaction liquids, especially in a recirculation system flowing through the reactor and said space. After every reaction stage the solid product obtained is optionally washed by water using a continuous flow of water through the reactor to remove the residual reaction liquids. Thereafter the solid end product is optionally dried, preferably in an air flow at a temperature of 40-100 ·C.
Description
2 ~ S 7 7 ~3 ~ PCT/FI90/00247 Method for manufacture of chitosan and other products from shells of organisms, especially marine organisms The invention relates to a msthod for manufacture of chitosan and other products, such as chitin and proteins, from shells of organisms, especially marine organisms.
There are methods of manufacturing chitin as well as chitosan, which subject the shells of marine organisms, such as crabs, shrimps or krills, to deproteinization, deminerali~ation and deacetylation in separate reaction systems. The well-known systems of deproteinization pxocesses are carried out by means of diluted aqueous solutions of alkaline metal hydroxides or their salts, usually in a temperature ranging from 20 to 120C for a period of 0.5-24 h or by means of an enzymatic method, in a stirring-disintegrating apparatus or in a tank without stirring. The demineralization process for obtaining chitin in well-known methods is carried out by means of aqueous acidic solutions, also with additives as hydrosulfite or sulfur dioxide, most . .
- often at room temperature in mixers or reactors equipped with rotatory mechanisms.
The deacetylation processes of chitin for obtaining chitosan in well-known systems are realized by subjecting the chitin to the action of concentrated aqueous alkaline metal hydroxide solutions, most often sodium hydroxide solution with 40-60 wt%
concentration at temperatures of 90~140C. The deacetylation is carried out in pressure reactors usually equipped with stirrers.
; 35 The well-known methods are described in a monography of Chitin, Pergamon Press, 1978; Australian Journal of Biological Science, volume 7, pages 168-178, 1954;
Journal of Americal Chemical Society, volume 79, WO91/05~08 PCT/Fl90/00247 ?. n ~
pages 5046-5049, 1957; Nature, volume 180, pages 40-41~
1957; Journal of Organic Chemistry, volume 23, pages 1990-1991, 1958; Norisho Suisan Koshusho Kenkyo Hokoku, volume 11, pages 339-406, 1962; Journal of organic Chemistry, volume 27, pages 1161-1163, 1962; Methods of Carbohydrate Chemistry, volume 5, pages 403-406, 1965; Chimica Industrie, Genie Chim., volume 99, pages 1241-1247, 1968; Fishing Technology, volume 11, number 1, pages 50-53, 1974; INFOFISH International, volume 5, pages 31-33, l9B7, and also in the conference proceedings of I-IV International Conferences on Chitin/Chitosan in USA, Japan, Italy and Norway at 1978, 1982, 1985 and 1988 as well as in U.S. Patents Nos. 2072771, 2040879, 3533940, 3862122, 3922260, 4066735, 4195175, 4199496, in Japanese Patents Nos. 75,126784 and 78,59700, International Ratent Application No. W086/06082 as well as Polish Patent No. 119931.
The well-known methods of manufacture of chitosan and other products from the shells of marine organisms require the using of sev~ral apparatuses equipped with stirrers and also requiring the transport of solid substances between particular technological process stages. The technological process is of long duration resulting at the same time in augmentation of production costs and in occupational health risk from the chemical substances used. Moreover, the chemical processes realized by the well-known methods, in spite of the use of stirring, do not create possibilities to obtain products with homogenous properties because of the heterogenous character of ; above processes.
- 35 The object of this invention is to provide a method for manufacture of chitosan and other products, such as chitin and proteins, from the shells of organisms, especially of marine type, in a single apparatus, by , , ~
~: .
WO9l/05808 2 ~ 6 7 7 PCT/FI~0/00247 1, deproteinization using alkaline solutions, demineralization using acidic solutions, as well as by deacetylation using concentrated alkaline solutions.
In accordance with a preferr~d embodiment of the method of the invention the manufacture of chitosan and other products from the shells of organisms, especially marine organisms, by deproteinization, demineralization and deacetylation, is characterized in that the shells of organisms, especially marine organisms, such as crabs or shrimps, are subjected to the continuous action of reaction liquids in a single apparatus of perforated type or equipped with perforated divisions, especially in a circulation system, whereby the reaction liquids flow through a reactor with a flow rate of 0.5-10000 volume parts per 1 weight part of solid product and 1 hour, whereby :: after each reaction stage the solid product obtained is optionally washed with water using a continuous system flowing through the reactor with a flow rate of 1-20000 volume parts per 1 weight part of solid product and 1 hour in order to remove the residual ;: reaction liquids, whereafter the chitosan obtained in - a solid form is eventually dried, preferably in air-:~ 25 flow conditions at a temperature of 40-100C.
According to a preferred embodiment of the invention, the manufacture of chitosan and other products is characterized in that the deproteinization is carried out by using alkaline solutions, especially aqueous alkaline metal hydroxide solutions or their salts, such as sodium hydroxide or sodium carbonate, having : a concentration of 0.1-10 wt%, at a temperature not lower than 10C for a time necessary to complete the removal of proteins, the demineralization is carried out either before or after the deproteinization stage by using aqueous acidic solutions, expecially inorganic acids, such as hydrochloric or sulfuric . :. ' :
W091/0~08 Q3 PCT/FI90/00247 ~a~
acids having a concentration of 0.1-20 wt% for a time necessary to dissolve the inorganic compounds, such as calcium and magnesium derivatives, at a temperature not lower than 10C, especially 20-lOO~C, whereafter the deacetylation is carried out by using concentrated alkaline solutions, especially aqueous alkaline metal hydroxide solutions or their salts, such as sodium or potassium hydroxides or their salts, having a concentration of 20-60 wt%, for a time ranging from 30 minutes to 25 hours at a temperature ranging from 60 to 140C.
The proteins from the alkaline solutions are recovered ~:
by reduction the pH to 3-6 by means of organic or ~15 inorganic acids, such as acetic, hydrochloric or sulfuric acids, especially having a concentration of 1-lQ wt%. The chitin obtained after demineralization is purified and optionally dried.
The fundamental advantage of the method according to the invention is the realization of all the processes, startingfrom deproteinizationthrough demineralization finally to deacetylation, including the purification as well, in a single apparatus, in which the substrate in a form of shells of oxganisms such as crabs, shrimps, krills or insects, constitutes a stationary phase whereas the reaction liquids as well as the washing water are acting in a continuous movement enhancing at the same time the effectivity of the :30 processes by reduction of the time of an individual operation as weil as by reduction of the concentration of the reagents used in comparison to well-known :~methods. Application of a closed circulation system reduces considerably the consumption of the reaction liquids.
., The advantaqe of the method according to the invention is the use of the continuous flow system of liquids ., .
,~, .
. ' , ' ' , ' .
WO~1/05808 PCT/FI90/00247 2~773~
without a necessity for stirring, which is dif~icult or even impossible to realize in a case oP raw materials used in the form of shells of marine organisms. Due to the flow of the reaction liquids the deproteinization, demineralization and deacetylation related to the production o~ proteins, chitin and chitosan, are facilitated.
As a result of the flow of alkaline solution in the deproteinization process, a dissolution of proteins present as a residue on the shells will take place.
In a method according to the invention, the rate o~
removal of the proteins is 2-3 times faster than in a conventional p~riodical method. At the same time it is possible to use alkaline solutions having lower concentration for removing of proteins, or to use a lower temperature in carrying out the process.
`~ Deproteinization in a method according to the invention ~-allows to obtain the proteins without their superfluous 20 degradation and having homogenous properties.
The demineralization in a method according to the invention by means of the flow of an acid solution, resulting in he removal of calcium compounds from 25 the shells, takes place where these compounds are existing in the shells in a form of insoluble carbonat~s and their removal takes place through conversion of these carbonates to suitable soluble salts. The method according to the invention increases 30 the effectivity of demineralization process by the order of 2-4 times in comparison to well known methods, as a result of a better penetration of the demineralizing liquids causing the acceleration of reaction, which leads firstly to the reduction of 35 process time and secondly to decreased energy ~consumption. The method according to the invention tallows to obtain chitin characterized by minimal content o~ ash, being below 0.5-1.0 wt%o ':
.:
. , .. :: :: -, ' wo 91/05~08 PCr/F190/00247 r~ ) 6 _~
The deacetylation process as a result of treatmet with alkaline solutions having ~ high concentration ranging from 20 to 60 wt% causes a deacetylation reaction of acetylamino groups of chitin to amine groups in chitosan. The process is carried out in order to obtain a product with homogenous properties and being soluble in an aqueous acetic acid solution.
A method according to the invention ensures a 2-3 times increment in effectivity of a deacetylation process as a result of better mass exchange caused by the continuous f low of the deacetylating solution and also by the augmentation of the deacetylation rate.
It is possible to obtain chitosan with correct properties as early as after 4 hours of deacetylation process by using 30-50 wt% concentrated sodium hydroxide solution at a temperature of 90-100C.
.
2 0 An advantage of a method according to the invention is also a possibility for effective purification of the products, resulting from a continuous washing f low using water, especially in a circulation system .
A possibility of drying of chitin or chitosan in a reactor by a pressurized air at higher temperature is also an advantage af f orded by the method .
A method according to the invention allows to reduce the production cost at least l. 5-2 times, based on a lower consumption of energy as well as chemicals and also on a lower cost of labour.
The chitosan, chitin and proteins obtained by the - method according to the invention are applied to the - 35 chemical industry, agriculture, medicine, pharmaceutical and cosmetic industry, paper industry, waste water treatment etc.
., . .
.
.:
, . ~ .
7 ~77~
A method for manufacture of chitosan and other products from the shells of organisms, especially marine, is realiz~d in an installatio~ shown schematically in the accompanying drawings, where Fig. 1 shows the installation having a reactor equipped with a perforated basket, and Fig. 2 shows an installation having a reactor equipped with perforated divisions.
The installation in Fig. 1 contains a reactor 1 in a ; form of a tank having a heating jacket 4, the reactor bein~ equipped with an immersed perforated basket 2 in which the shells 3 are located. The reactor 1 is joined to a draining or outlet pipe 5 located in the reactor outside the basket and being of a controllable depth of immersion. The pipe is connected through a pump 6 and through subsequent valves 7 and 9 to an inlet or conveying pipe 10 leading back to the reactor into the basket and having its outlet end near the bottom of the basket. A draining and supply pipe is connected through a valve 8 to the outlet pipe 5 from the reactor 1 and to the inlet pipe 10 leading tc, the reactor, the junction point being between the valves 7 and-9. A branch supply pipe containing a valve 11 is connected to the pipe 10 between the valve ~ and ~he reactor.
: .
The action of tha above installation is as following:
a suitable amount of shells 3 is introduced into the ~ perforated basket 2 and the basket is inserted into the - reactor 1. The deproteinization liquid is introduced into the reactor 1 after opening of the valves 8 and 9, and after closing of the valve 8 and opening of the valve 7 and starting of the pump ~, the removal of proteins will be carried on by recirculating the reaction liquid through the pipes 5 and 10 optionally :
:', ,~ ', ' ', ' . ' ' ' .
WOgl/05~08 ~ PCT/Fl90/00247 ~r~
by heating the reactor simultaneously. The inlet end of the pipe is located close to the liquid surface of the reactor during the recirculating. The valve 9 is closed after the deproteinization is completed;
whereafter the valve 8 is opened, and the pip~ 5 is lowered deeper into the reactor 1 taking away the proteinaceous solution into a suitable tank. Next the valve 9 is opened and washing water is introduced through the valve 8 and valve 9, and after closing of the valve 8 the purification process is carried on. The purification process can be carried on also with a continuous flow of the washing water through the valve 11. The liguid can be recirculated also partly -by taking of the liquid through the valve 8 only partly. A~ter the purification and water removal the de~ineralization as well as the deacetylation liquids are introduced in turn followed by an application of suitable water purification operations.
The installation in Fig. 2 contains a reactor 1 in the ~orm of a tank equipped with a horizontal `perforated division or partition 2 restricting the area of the shells 3 to the upper part of the reactor.
The area outside the shells below the partition 2 is 25 joined to a valve 5 at the bottom of the reactor and to a draining pipe 6 having a pump 7. In the direction of flow, the pump is followed by a system of valves 8, 9 and 10, where the valve 9 has the same Punction as the valve 8 in Fig.9, being situated in a supply 30 and drainage line joined to the recirculation line at the junction point between the valves 8 and 10. The pump 7 is joined through the valves 8 and 10 to the reactor 1, where the shells 3 are located, through a 7 conveying pipe 11 to which is connected a supply 35 branch pipe having a valve 12. The outlet of the pipe 11 is located above the shells 3 in the reactor. The action of the installation shown in Fig. 2 is analogous ; to the installation in Fig. 1.
. ~ . .
. . . : ' , ' .
,, ' ', ' - '. ' ' ' ' . ' ~ `' ~':
~, '.
wo91/os808 PCT/Fl90/00247 2 ~ 8 ~
The well-known methods for manufacture of chitosan and other products from the shells up to now have comprised a stationary system for recovery of proteins, chitin and chitosan, as described for example in US.
Pat. No. 4,199,496. The following processes as - deproteinization - demineralization - deacetylation have always been realized in stationary conditions in separate apparatuses. Penetration rate by reaction liquid media, reaction effectivity as well as properties of products obtained have been low in these conventional methods. The new method for ; manufacture of chitosan and other products as chitin and proteins according to the present invention, utilizes the continuous action of reacting liquid media penetrating solid wastes with much higher effectivity of reactions of deproteinization, demineralization as well as deacetylation. In addition, the processes of chitosan, chitin and proteins manufacture need to be realized only in one single apparatus where the shells are placed in the beginning and the citosan is removed in the end of the process ` series.
.
The action of reaction media in the new system is better than in well-known methods. In the following table is presented some comparative data between the older method and the method of the present invention.
':
.; .
. ' ' ' ~'. ' ' ~ .
, . ' ~' , WO ~1/05808 PCr/F190/00247 ctJ~J~3 10 Table Comparison of optimal conditions for - processing of shells Pro~ Opkimal conditions Wbll-k~n methods New method 1. ~e~rote~ization NaOH conc. 0,5~ NaOH conc. 0,5%
tEmp. about 100C ~.max. 40-60C
or higher 2. D~Ln~ralization HCl conc. 5-10% HCl c~nc. 5-10%
t~ 10-16h tLme max. 4-6 h
There are methods of manufacturing chitin as well as chitosan, which subject the shells of marine organisms, such as crabs, shrimps or krills, to deproteinization, deminerali~ation and deacetylation in separate reaction systems. The well-known systems of deproteinization pxocesses are carried out by means of diluted aqueous solutions of alkaline metal hydroxides or their salts, usually in a temperature ranging from 20 to 120C for a period of 0.5-24 h or by means of an enzymatic method, in a stirring-disintegrating apparatus or in a tank without stirring. The demineralization process for obtaining chitin in well-known methods is carried out by means of aqueous acidic solutions, also with additives as hydrosulfite or sulfur dioxide, most . .
- often at room temperature in mixers or reactors equipped with rotatory mechanisms.
The deacetylation processes of chitin for obtaining chitosan in well-known systems are realized by subjecting the chitin to the action of concentrated aqueous alkaline metal hydroxide solutions, most often sodium hydroxide solution with 40-60 wt%
concentration at temperatures of 90~140C. The deacetylation is carried out in pressure reactors usually equipped with stirrers.
; 35 The well-known methods are described in a monography of Chitin, Pergamon Press, 1978; Australian Journal of Biological Science, volume 7, pages 168-178, 1954;
Journal of Americal Chemical Society, volume 79, WO91/05~08 PCT/Fl90/00247 ?. n ~
pages 5046-5049, 1957; Nature, volume 180, pages 40-41~
1957; Journal of Organic Chemistry, volume 23, pages 1990-1991, 1958; Norisho Suisan Koshusho Kenkyo Hokoku, volume 11, pages 339-406, 1962; Journal of organic Chemistry, volume 27, pages 1161-1163, 1962; Methods of Carbohydrate Chemistry, volume 5, pages 403-406, 1965; Chimica Industrie, Genie Chim., volume 99, pages 1241-1247, 1968; Fishing Technology, volume 11, number 1, pages 50-53, 1974; INFOFISH International, volume 5, pages 31-33, l9B7, and also in the conference proceedings of I-IV International Conferences on Chitin/Chitosan in USA, Japan, Italy and Norway at 1978, 1982, 1985 and 1988 as well as in U.S. Patents Nos. 2072771, 2040879, 3533940, 3862122, 3922260, 4066735, 4195175, 4199496, in Japanese Patents Nos. 75,126784 and 78,59700, International Ratent Application No. W086/06082 as well as Polish Patent No. 119931.
The well-known methods of manufacture of chitosan and other products from the shells of marine organisms require the using of sev~ral apparatuses equipped with stirrers and also requiring the transport of solid substances between particular technological process stages. The technological process is of long duration resulting at the same time in augmentation of production costs and in occupational health risk from the chemical substances used. Moreover, the chemical processes realized by the well-known methods, in spite of the use of stirring, do not create possibilities to obtain products with homogenous properties because of the heterogenous character of ; above processes.
- 35 The object of this invention is to provide a method for manufacture of chitosan and other products, such as chitin and proteins, from the shells of organisms, especially of marine type, in a single apparatus, by , , ~
~: .
WO9l/05808 2 ~ 6 7 7 PCT/FI~0/00247 1, deproteinization using alkaline solutions, demineralization using acidic solutions, as well as by deacetylation using concentrated alkaline solutions.
In accordance with a preferr~d embodiment of the method of the invention the manufacture of chitosan and other products from the shells of organisms, especially marine organisms, by deproteinization, demineralization and deacetylation, is characterized in that the shells of organisms, especially marine organisms, such as crabs or shrimps, are subjected to the continuous action of reaction liquids in a single apparatus of perforated type or equipped with perforated divisions, especially in a circulation system, whereby the reaction liquids flow through a reactor with a flow rate of 0.5-10000 volume parts per 1 weight part of solid product and 1 hour, whereby :: after each reaction stage the solid product obtained is optionally washed with water using a continuous system flowing through the reactor with a flow rate of 1-20000 volume parts per 1 weight part of solid product and 1 hour in order to remove the residual ;: reaction liquids, whereafter the chitosan obtained in - a solid form is eventually dried, preferably in air-:~ 25 flow conditions at a temperature of 40-100C.
According to a preferred embodiment of the invention, the manufacture of chitosan and other products is characterized in that the deproteinization is carried out by using alkaline solutions, especially aqueous alkaline metal hydroxide solutions or their salts, such as sodium hydroxide or sodium carbonate, having : a concentration of 0.1-10 wt%, at a temperature not lower than 10C for a time necessary to complete the removal of proteins, the demineralization is carried out either before or after the deproteinization stage by using aqueous acidic solutions, expecially inorganic acids, such as hydrochloric or sulfuric . :. ' :
W091/0~08 Q3 PCT/FI90/00247 ~a~
acids having a concentration of 0.1-20 wt% for a time necessary to dissolve the inorganic compounds, such as calcium and magnesium derivatives, at a temperature not lower than 10C, especially 20-lOO~C, whereafter the deacetylation is carried out by using concentrated alkaline solutions, especially aqueous alkaline metal hydroxide solutions or their salts, such as sodium or potassium hydroxides or their salts, having a concentration of 20-60 wt%, for a time ranging from 30 minutes to 25 hours at a temperature ranging from 60 to 140C.
The proteins from the alkaline solutions are recovered ~:
by reduction the pH to 3-6 by means of organic or ~15 inorganic acids, such as acetic, hydrochloric or sulfuric acids, especially having a concentration of 1-lQ wt%. The chitin obtained after demineralization is purified and optionally dried.
The fundamental advantage of the method according to the invention is the realization of all the processes, startingfrom deproteinizationthrough demineralization finally to deacetylation, including the purification as well, in a single apparatus, in which the substrate in a form of shells of oxganisms such as crabs, shrimps, krills or insects, constitutes a stationary phase whereas the reaction liquids as well as the washing water are acting in a continuous movement enhancing at the same time the effectivity of the :30 processes by reduction of the time of an individual operation as weil as by reduction of the concentration of the reagents used in comparison to well-known :~methods. Application of a closed circulation system reduces considerably the consumption of the reaction liquids.
., The advantaqe of the method according to the invention is the use of the continuous flow system of liquids ., .
,~, .
. ' , ' ' , ' .
WO~1/05808 PCT/FI90/00247 2~773~
without a necessity for stirring, which is dif~icult or even impossible to realize in a case oP raw materials used in the form of shells of marine organisms. Due to the flow of the reaction liquids the deproteinization, demineralization and deacetylation related to the production o~ proteins, chitin and chitosan, are facilitated.
As a result of the flow of alkaline solution in the deproteinization process, a dissolution of proteins present as a residue on the shells will take place.
In a method according to the invention, the rate o~
removal of the proteins is 2-3 times faster than in a conventional p~riodical method. At the same time it is possible to use alkaline solutions having lower concentration for removing of proteins, or to use a lower temperature in carrying out the process.
`~ Deproteinization in a method according to the invention ~-allows to obtain the proteins without their superfluous 20 degradation and having homogenous properties.
The demineralization in a method according to the invention by means of the flow of an acid solution, resulting in he removal of calcium compounds from 25 the shells, takes place where these compounds are existing in the shells in a form of insoluble carbonat~s and their removal takes place through conversion of these carbonates to suitable soluble salts. The method according to the invention increases 30 the effectivity of demineralization process by the order of 2-4 times in comparison to well known methods, as a result of a better penetration of the demineralizing liquids causing the acceleration of reaction, which leads firstly to the reduction of 35 process time and secondly to decreased energy ~consumption. The method according to the invention tallows to obtain chitin characterized by minimal content o~ ash, being below 0.5-1.0 wt%o ':
.:
. , .. :: :: -, ' wo 91/05~08 PCr/F190/00247 r~ ) 6 _~
The deacetylation process as a result of treatmet with alkaline solutions having ~ high concentration ranging from 20 to 60 wt% causes a deacetylation reaction of acetylamino groups of chitin to amine groups in chitosan. The process is carried out in order to obtain a product with homogenous properties and being soluble in an aqueous acetic acid solution.
A method according to the invention ensures a 2-3 times increment in effectivity of a deacetylation process as a result of better mass exchange caused by the continuous f low of the deacetylating solution and also by the augmentation of the deacetylation rate.
It is possible to obtain chitosan with correct properties as early as after 4 hours of deacetylation process by using 30-50 wt% concentrated sodium hydroxide solution at a temperature of 90-100C.
.
2 0 An advantage of a method according to the invention is also a possibility for effective purification of the products, resulting from a continuous washing f low using water, especially in a circulation system .
A possibility of drying of chitin or chitosan in a reactor by a pressurized air at higher temperature is also an advantage af f orded by the method .
A method according to the invention allows to reduce the production cost at least l. 5-2 times, based on a lower consumption of energy as well as chemicals and also on a lower cost of labour.
The chitosan, chitin and proteins obtained by the - method according to the invention are applied to the - 35 chemical industry, agriculture, medicine, pharmaceutical and cosmetic industry, paper industry, waste water treatment etc.
., . .
.
.:
, . ~ .
7 ~77~
A method for manufacture of chitosan and other products from the shells of organisms, especially marine, is realiz~d in an installatio~ shown schematically in the accompanying drawings, where Fig. 1 shows the installation having a reactor equipped with a perforated basket, and Fig. 2 shows an installation having a reactor equipped with perforated divisions.
The installation in Fig. 1 contains a reactor 1 in a ; form of a tank having a heating jacket 4, the reactor bein~ equipped with an immersed perforated basket 2 in which the shells 3 are located. The reactor 1 is joined to a draining or outlet pipe 5 located in the reactor outside the basket and being of a controllable depth of immersion. The pipe is connected through a pump 6 and through subsequent valves 7 and 9 to an inlet or conveying pipe 10 leading back to the reactor into the basket and having its outlet end near the bottom of the basket. A draining and supply pipe is connected through a valve 8 to the outlet pipe 5 from the reactor 1 and to the inlet pipe 10 leading tc, the reactor, the junction point being between the valves 7 and-9. A branch supply pipe containing a valve 11 is connected to the pipe 10 between the valve ~ and ~he reactor.
: .
The action of tha above installation is as following:
a suitable amount of shells 3 is introduced into the ~ perforated basket 2 and the basket is inserted into the - reactor 1. The deproteinization liquid is introduced into the reactor 1 after opening of the valves 8 and 9, and after closing of the valve 8 and opening of the valve 7 and starting of the pump ~, the removal of proteins will be carried on by recirculating the reaction liquid through the pipes 5 and 10 optionally :
:', ,~ ', ' ', ' . ' ' ' .
WOgl/05~08 ~ PCT/Fl90/00247 ~r~
by heating the reactor simultaneously. The inlet end of the pipe is located close to the liquid surface of the reactor during the recirculating. The valve 9 is closed after the deproteinization is completed;
whereafter the valve 8 is opened, and the pip~ 5 is lowered deeper into the reactor 1 taking away the proteinaceous solution into a suitable tank. Next the valve 9 is opened and washing water is introduced through the valve 8 and valve 9, and after closing of the valve 8 the purification process is carried on. The purification process can be carried on also with a continuous flow of the washing water through the valve 11. The liguid can be recirculated also partly -by taking of the liquid through the valve 8 only partly. A~ter the purification and water removal the de~ineralization as well as the deacetylation liquids are introduced in turn followed by an application of suitable water purification operations.
The installation in Fig. 2 contains a reactor 1 in the ~orm of a tank equipped with a horizontal `perforated division or partition 2 restricting the area of the shells 3 to the upper part of the reactor.
The area outside the shells below the partition 2 is 25 joined to a valve 5 at the bottom of the reactor and to a draining pipe 6 having a pump 7. In the direction of flow, the pump is followed by a system of valves 8, 9 and 10, where the valve 9 has the same Punction as the valve 8 in Fig.9, being situated in a supply 30 and drainage line joined to the recirculation line at the junction point between the valves 8 and 10. The pump 7 is joined through the valves 8 and 10 to the reactor 1, where the shells 3 are located, through a 7 conveying pipe 11 to which is connected a supply 35 branch pipe having a valve 12. The outlet of the pipe 11 is located above the shells 3 in the reactor. The action of the installation shown in Fig. 2 is analogous ; to the installation in Fig. 1.
. ~ . .
. . . : ' , ' .
,, ' ', ' - '. ' ' ' ' . ' ~ `' ~':
~, '.
wo91/os808 PCT/Fl90/00247 2 ~ 8 ~
The well-known methods for manufacture of chitosan and other products from the shells up to now have comprised a stationary system for recovery of proteins, chitin and chitosan, as described for example in US.
Pat. No. 4,199,496. The following processes as - deproteinization - demineralization - deacetylation have always been realized in stationary conditions in separate apparatuses. Penetration rate by reaction liquid media, reaction effectivity as well as properties of products obtained have been low in these conventional methods. The new method for ; manufacture of chitosan and other products as chitin and proteins according to the present invention, utilizes the continuous action of reacting liquid media penetrating solid wastes with much higher effectivity of reactions of deproteinization, demineralization as well as deacetylation. In addition, the processes of chitosan, chitin and proteins manufacture need to be realized only in one single apparatus where the shells are placed in the beginning and the citosan is removed in the end of the process ` series.
.
The action of reaction media in the new system is better than in well-known methods. In the following table is presented some comparative data between the older method and the method of the present invention.
':
.; .
. ' ' ' ~'. ' ' ~ .
, . ' ~' , WO ~1/05808 PCr/F190/00247 ctJ~J~3 10 Table Comparison of optimal conditions for - processing of shells Pro~ Opkimal conditions Wbll-k~n methods New method 1. ~e~rote~ization NaOH conc. 0,5~ NaOH conc. 0,5%
tEmp. about 100C ~.max. 40-60C
or higher 2. D~Ln~ralization HCl conc. 5-10% HCl c~nc. 5-10%
t~ 10-16h tLme max. 4-6 h
3. Deaoetylation NaOH conc. 40-60% NaOH con~. 40-60%
min. 100-140C, max. 100-110C
pref~ly high withou~ pr~re ?
mLn. 10-20h max. 4-8h . .
.
The chitin and chitosan obtained according to the new method is more homogenous in properties in comparison to products obtained by well~known methods. The ash content in chitosan obtained by new method is lower than 1%, usually 0.1-0.5%, whereas the level of 1% of ash is possible to be obtained by well-known methods using the drastic conditions mainly in a demineralization stage, taking usually 10-16h in comparison to max. 4-6h in the new method.
.
: 30 The invention is explained further in the following examples which do not restrict the scope of claims.
Example 1 .
12.16 weight parts of Norwegian shrimp shells containing 1.0 wt% of moisture and 0.88 wt~ ~f nitrogen, and 400 volume parts of 2.5~ aqueous sodium hydroxide solution were introduced into the reactor :, .~ .
:. . . ..
, . . .. .
.. , :- . , ,~ . . , ~ . .
- - :
.... .
.' . , ', ~, '' ' ' ' , . ' ' ' .
.: , .
.. . .
WO ~1l/0580~ PCl/F190/00247 7 7 ~ 8 shown in Fig. 1. Deproteinization was carried out at a temperature of 300c and for a period of 1.5 h in the circulation system using a flow rate of 4934 volume parts per 1 weight part of shells and 1 hour, whereafter the alkaline solution containing dissolved proteins with a red colour, d~ = 1.154 g/cm3 and pH = 11.6, was continuously taken away. Next the shrimp shells were continuously washed by water with a flow rate of 6000 volume parts per 1 weight part of shells and 1 hour, whereafter 350 volume parts of 10% aqueous hydrochloric acid solution was introduced into the installation. The demineralization was carried out using a continuous flow of hydrochloric acid solution with a flow rate of 5000 volume parts per l weight part of shells and 1 hour at a temperature of 40C
for a period of 2 h, then the excess of hydrochloric acid solution was washed off at a temperature of 20-300C using a wa~er flow rate of 500 volume parts per 1 weight part of chitin and 1 hour to obtain a neutral reaction of eluate, whereafter the chitin was dried at a temperature of 90C.
; 3.1 weight parts of chitin in a solid form with a light yellow colour was obtained. The product was characterized by a water retention value (WRV) of 87.6%, nitrogen content of 5.5 wt%, ash content of 0.28 wt%. The chitin was not soluble in 4% aqueous acetic acid solution. IR studies showed the absorption band at the frequency of 1650 cm~l characteristic for amide groups.
2.5 weight parts of chitin obtained was introduced in a reactor shown in Fig. 1 and on it 200 volume parts of 35% aqueous sodium hydroxide solution was poured.
The deacetylation was carried on using a continuous - flow with a flow rate of 15 volume parts per 1 weight part of chitin and 1 hour at a temperature of 75C
for 20 h~ Next the excess of sodium hydroxide solution ,. : ' ' ' ' ~ ~ .
WO 91/05808~ ~ r~ ~ ~) PCI /F190/00247 was washed off continuously at a temperature of 20-30c using a ~low rate of 500 volume parts per 1 weight part of chitin and 1 hour to obtain a neutral reaction. After the removal of water, the product was dried by pressurized air at a temperature of 70c.
2.1 waight parts of chitosan with a white colour was obtained. The product was characterized by the WRV of 95.5%, average molecular weight Mw of 205000, deacetylation degree of 69.5% and nitro~en content of 6.9 wt%. IR studies showed the absorption band at the ~raquency of 1570 cm~1 characteristic for amine groups.
Example 2 27.72 weight parts of Norwegian shrimp shells containing 1 wt% of moisture and 0.88 wt% of nitrogen and 800 volume parts of 5 wt% aqueous sodium hydroxide solution were introduced into the reactor as in Example 1. The deproteinization was carried on at a temperature of 60OC for 1 h in a circulation system having a flow rate of 2480 volume parts per 1 weight part of shells and 1 hour, whereafter the alkaline solution of proteins with red colour, d~ = 1.143 g/cm3, pH =
11.7, was drained out.
The protein solution was treated on continuous stirring by 5% hydrochloric acid solution to obtain pH = 4Ø
0.6 weight parts of proteins with a light red colour, containing 1.83 wt% nitrogen, characterized by the presence of aspartic acid, glutamic acid, alanine, glycine, tyrosine, fenylalanine, lysine, arinine, threonine, serine, isoleucine and leucine was obtained.
~ 35 Next the shells were continuously washed by water I!
with a flow rate of 9000 volume parts per 1 weight part of shells and 1 hour. Subsequently, 600 volume parts of 10% aqueous sulfuric acid solution was ::~
; .
. . .
'. ' ' !
"` ' ' ' ~ ;
. : ' ' ' ~ ' ,' .
WO91/05808 13 2 ~ ~ 7 7 PC~/FI90/00247 introduced into the reactor. Demineralization was carried out by means of a continuous ~low with a flow rate of 1210 volume parts per l weight part of shells and 1 hour at a temperature of 40C for 2 h, whereafter the excess of sulfuric acid solution was washed out at a temperature 20-30C using a flow rate of 1200 volume parts per 1 weight part of chitin and 1 hour to obtain a neutral pH of eluate. Next 50U volume parts of 30% aqueous potassium hydroxide solution containing 1.5 wt% of potassium carbonate and 0.5 wt%
of sodium carbonate was introduced. Deacetylation was carried out at a temperature of 100-105C for a period of 4 h using a flow rate of 7200 volume parts per 1 weight part of chitin and l hour and then, after purification, the product was dried by pressurized air at a temperature of 100C.
' 5.35 weight parts of chitosan with a light yellow colour was obtained. The chitosan was characterized 20 by nitrogen content of 5.9 wt%, WRV f 73-4%, Mw =
169060, deacetylation degree of 73.4~ and a good solubility in a 4% aqueous acetic acid solution. IR
studies showed the absorption band at the frequency of 1560 cm~l characteristic of amine groups.
~xamDle 3 .~ .
21.49 weight parts of Norwegian shrimp shells with properties as in Example 1 and 900 volume parts of 1%
aqueous sodium hydroxide solution was introduced into the reactor shown in Fig. 1. Deproteinization at a temperature of 50C for 1.5 h in a circulation system using a flow rate of 9800 volume parts per 1 weight part of shells and 1 hour was carried on, whareafter ~ 35 the proteins containing solution with a red colour, d~ = 1.112 g/cm3, pH = 1~.05 was drained out. Next the product obtained was washed by water using a flow rate of 4200 volume parts per 1 weight part of shells ., ' :
, .
` ' ' , . .
W09l/0580~ PCT/Fl90/00247 ~r~ 14 and l hour, whereafter 700 volume parts of 10% aqueous hydrochloric acid solution were introduced.
Demineralization at a temperature of 20-23C for 280 minutes using a flow rate of lo volume parts per l weight part of shells and 1 hour was carried out.
Next the excess of hydrochloric acid solution was washed out with water at room temperature using a flow rate of 1000 volume parts per l weight part of chitin and 1 hour. After the water had drained out, 600 volume parts of 50% aqueous sodium hydroxide solution were introduced into the reactor and the deacetylation was carried out using continuous circulation at a temperature of 110-120C for 330 minutes using a flow rate of 2400 volume parts per 1 weight part of chitin and 1 hour. The product obtained after the washing was dried at a temperature of 80C.
:, 3.3 weight parts of chitosan with white colour characterized by WRV of 87.6%, nitrogen content of 6.2%, Mw of 75690, deacetylation degree of 78.2%, ash content of 0.93 wt~ and very good solubility in 4%
aqueous acetic acid solution was obtained. IR studies -~ showed the absorption band at the frequence of 1580 cm~l characteristic of amine groups.
Exam~le 4 :
` 31.73 weight parts of Norwegian shrimp shells with properties as in Example 1 and 800 volume parts of 5%
aqueous sodium hydroxide solution were introduced into the reactor presented in Fig. 1. Deproteinization at a temperature of 50C for 2 h with a flow rate of ~ -7560 volume parts per 1 weight part of shells and 1 hour was carried on, whereafter the alkaline solution containing proteins with a red colour, d2~ = 1.159 g/cm3, pH = 11.7 was taken off. Next the product was washed continuously by water to obtain a pH of 7 . . .
:, , .
'' "''"'' .' ~ ' ..
. ' , WO9l/05808 PCT/Fl90/00247 20~77~
using a flow rate of 1150 volume parts per 1 weight part of shells and 1 hour, whereafter the water was taken out from the reactor.
Demineralization was carried out by means of 800 volume parts of 10% aqueous hydrochloric acid solution for 2 h at a temperature of 40C using a flow rate of ` 125 volu~e parts per 1 weight part of shells and 1 hour. Next the excess of hydrochloric acid solution was washed out by water with a flow rate of 15200 volume parts per 1 weight part of chitin and 1 hour to obtain a pH of 7Ø After water had drained out, 600 volume parts of 40% aqueous sodium hydroxide solution was introduced into the reactor and the deacetylation at a temperature of 90c for 6 h as well as at a temperature of 100C for next 1 h was carried on. The product obtained after purification was dried at a temperature of 90C.
6.3 weight parts of chitosan with a white colour characterized by deacetylation degree of 85.8%, ash contents of 0.83 Wt4, nitrogen contents of 6.1 wt%, WRV of 106.6%, Mw of 184800 and a good solubility in
min. 100-140C, max. 100-110C
pref~ly high withou~ pr~re ?
mLn. 10-20h max. 4-8h . .
.
The chitin and chitosan obtained according to the new method is more homogenous in properties in comparison to products obtained by well~known methods. The ash content in chitosan obtained by new method is lower than 1%, usually 0.1-0.5%, whereas the level of 1% of ash is possible to be obtained by well-known methods using the drastic conditions mainly in a demineralization stage, taking usually 10-16h in comparison to max. 4-6h in the new method.
.
: 30 The invention is explained further in the following examples which do not restrict the scope of claims.
Example 1 .
12.16 weight parts of Norwegian shrimp shells containing 1.0 wt% of moisture and 0.88 wt~ ~f nitrogen, and 400 volume parts of 2.5~ aqueous sodium hydroxide solution were introduced into the reactor :, .~ .
:. . . ..
, . . .. .
.. , :- . , ,~ . . , ~ . .
- - :
.... .
.' . , ', ~, '' ' ' ' , . ' ' ' .
.: , .
.. . .
WO ~1l/0580~ PCl/F190/00247 7 7 ~ 8 shown in Fig. 1. Deproteinization was carried out at a temperature of 300c and for a period of 1.5 h in the circulation system using a flow rate of 4934 volume parts per 1 weight part of shells and 1 hour, whereafter the alkaline solution containing dissolved proteins with a red colour, d~ = 1.154 g/cm3 and pH = 11.6, was continuously taken away. Next the shrimp shells were continuously washed by water with a flow rate of 6000 volume parts per 1 weight part of shells and 1 hour, whereafter 350 volume parts of 10% aqueous hydrochloric acid solution was introduced into the installation. The demineralization was carried out using a continuous flow of hydrochloric acid solution with a flow rate of 5000 volume parts per l weight part of shells and 1 hour at a temperature of 40C
for a period of 2 h, then the excess of hydrochloric acid solution was washed off at a temperature of 20-300C using a wa~er flow rate of 500 volume parts per 1 weight part of chitin and 1 hour to obtain a neutral reaction of eluate, whereafter the chitin was dried at a temperature of 90C.
; 3.1 weight parts of chitin in a solid form with a light yellow colour was obtained. The product was characterized by a water retention value (WRV) of 87.6%, nitrogen content of 5.5 wt%, ash content of 0.28 wt%. The chitin was not soluble in 4% aqueous acetic acid solution. IR studies showed the absorption band at the frequency of 1650 cm~l characteristic for amide groups.
2.5 weight parts of chitin obtained was introduced in a reactor shown in Fig. 1 and on it 200 volume parts of 35% aqueous sodium hydroxide solution was poured.
The deacetylation was carried on using a continuous - flow with a flow rate of 15 volume parts per 1 weight part of chitin and 1 hour at a temperature of 75C
for 20 h~ Next the excess of sodium hydroxide solution ,. : ' ' ' ' ~ ~ .
WO 91/05808~ ~ r~ ~ ~) PCI /F190/00247 was washed off continuously at a temperature of 20-30c using a ~low rate of 500 volume parts per 1 weight part of chitin and 1 hour to obtain a neutral reaction. After the removal of water, the product was dried by pressurized air at a temperature of 70c.
2.1 waight parts of chitosan with a white colour was obtained. The product was characterized by the WRV of 95.5%, average molecular weight Mw of 205000, deacetylation degree of 69.5% and nitro~en content of 6.9 wt%. IR studies showed the absorption band at the ~raquency of 1570 cm~1 characteristic for amine groups.
Example 2 27.72 weight parts of Norwegian shrimp shells containing 1 wt% of moisture and 0.88 wt% of nitrogen and 800 volume parts of 5 wt% aqueous sodium hydroxide solution were introduced into the reactor as in Example 1. The deproteinization was carried on at a temperature of 60OC for 1 h in a circulation system having a flow rate of 2480 volume parts per 1 weight part of shells and 1 hour, whereafter the alkaline solution of proteins with red colour, d~ = 1.143 g/cm3, pH =
11.7, was drained out.
The protein solution was treated on continuous stirring by 5% hydrochloric acid solution to obtain pH = 4Ø
0.6 weight parts of proteins with a light red colour, containing 1.83 wt% nitrogen, characterized by the presence of aspartic acid, glutamic acid, alanine, glycine, tyrosine, fenylalanine, lysine, arinine, threonine, serine, isoleucine and leucine was obtained.
~ 35 Next the shells were continuously washed by water I!
with a flow rate of 9000 volume parts per 1 weight part of shells and 1 hour. Subsequently, 600 volume parts of 10% aqueous sulfuric acid solution was ::~
; .
. . .
'. ' ' !
"` ' ' ' ~ ;
. : ' ' ' ~ ' ,' .
WO91/05808 13 2 ~ ~ 7 7 PC~/FI90/00247 introduced into the reactor. Demineralization was carried out by means of a continuous ~low with a flow rate of 1210 volume parts per l weight part of shells and 1 hour at a temperature of 40C for 2 h, whereafter the excess of sulfuric acid solution was washed out at a temperature 20-30C using a flow rate of 1200 volume parts per 1 weight part of chitin and 1 hour to obtain a neutral pH of eluate. Next 50U volume parts of 30% aqueous potassium hydroxide solution containing 1.5 wt% of potassium carbonate and 0.5 wt%
of sodium carbonate was introduced. Deacetylation was carried out at a temperature of 100-105C for a period of 4 h using a flow rate of 7200 volume parts per 1 weight part of chitin and l hour and then, after purification, the product was dried by pressurized air at a temperature of 100C.
' 5.35 weight parts of chitosan with a light yellow colour was obtained. The chitosan was characterized 20 by nitrogen content of 5.9 wt%, WRV f 73-4%, Mw =
169060, deacetylation degree of 73.4~ and a good solubility in a 4% aqueous acetic acid solution. IR
studies showed the absorption band at the frequency of 1560 cm~l characteristic of amine groups.
~xamDle 3 .~ .
21.49 weight parts of Norwegian shrimp shells with properties as in Example 1 and 900 volume parts of 1%
aqueous sodium hydroxide solution was introduced into the reactor shown in Fig. 1. Deproteinization at a temperature of 50C for 1.5 h in a circulation system using a flow rate of 9800 volume parts per 1 weight part of shells and 1 hour was carried on, whareafter ~ 35 the proteins containing solution with a red colour, d~ = 1.112 g/cm3, pH = 1~.05 was drained out. Next the product obtained was washed by water using a flow rate of 4200 volume parts per 1 weight part of shells ., ' :
, .
` ' ' , . .
W09l/0580~ PCT/Fl90/00247 ~r~ 14 and l hour, whereafter 700 volume parts of 10% aqueous hydrochloric acid solution were introduced.
Demineralization at a temperature of 20-23C for 280 minutes using a flow rate of lo volume parts per l weight part of shells and 1 hour was carried out.
Next the excess of hydrochloric acid solution was washed out with water at room temperature using a flow rate of 1000 volume parts per l weight part of chitin and 1 hour. After the water had drained out, 600 volume parts of 50% aqueous sodium hydroxide solution were introduced into the reactor and the deacetylation was carried out using continuous circulation at a temperature of 110-120C for 330 minutes using a flow rate of 2400 volume parts per 1 weight part of chitin and 1 hour. The product obtained after the washing was dried at a temperature of 80C.
:, 3.3 weight parts of chitosan with white colour characterized by WRV of 87.6%, nitrogen content of 6.2%, Mw of 75690, deacetylation degree of 78.2%, ash content of 0.93 wt~ and very good solubility in 4%
aqueous acetic acid solution was obtained. IR studies -~ showed the absorption band at the frequence of 1580 cm~l characteristic of amine groups.
Exam~le 4 :
` 31.73 weight parts of Norwegian shrimp shells with properties as in Example 1 and 800 volume parts of 5%
aqueous sodium hydroxide solution were introduced into the reactor presented in Fig. 1. Deproteinization at a temperature of 50C for 2 h with a flow rate of ~ -7560 volume parts per 1 weight part of shells and 1 hour was carried on, whereafter the alkaline solution containing proteins with a red colour, d2~ = 1.159 g/cm3, pH = 11.7 was taken off. Next the product was washed continuously by water to obtain a pH of 7 . . .
:, , .
'' "''"'' .' ~ ' ..
. ' , WO9l/05808 PCT/Fl90/00247 20~77~
using a flow rate of 1150 volume parts per 1 weight part of shells and 1 hour, whereafter the water was taken out from the reactor.
Demineralization was carried out by means of 800 volume parts of 10% aqueous hydrochloric acid solution for 2 h at a temperature of 40C using a flow rate of ` 125 volu~e parts per 1 weight part of shells and 1 hour. Next the excess of hydrochloric acid solution was washed out by water with a flow rate of 15200 volume parts per 1 weight part of chitin and 1 hour to obtain a pH of 7Ø After water had drained out, 600 volume parts of 40% aqueous sodium hydroxide solution was introduced into the reactor and the deacetylation at a temperature of 90c for 6 h as well as at a temperature of 100C for next 1 h was carried on. The product obtained after purification was dried at a temperature of 90C.
6.3 weight parts of chitosan with a white colour characterized by deacetylation degree of 85.8%, ash contents of 0.83 Wt4, nitrogen contents of 6.1 wt%, WRV of 106.6%, Mw of 184800 and a good solubility in
4~ aqueous acetic acid solution was sbtained. IR
studies showed the absorption band at the frequency of 1560 cm~1 characteristic of amine groups.
Exam~le 5 32.5 weight parts of milled crab shells characterized by nitrogen contents of 0.7 wt~, and 800 volume parts of 5~ aqueous hydrochloric acid solution were introduced into the reactor presented in Fig. 2.
Demineralization at a temperature of 70 for 90 minutes using a flow rate of 1580 volume parts per l weight part of shells and 1 hour was carried out, whereafter the acid solution was taken off and the residues were continuously washed by water with a flow rate of 5050 WO91/05808 PCT/Fl90/00247 ~o~ume parts per 1 weight part of shPlls and 1 hour.
After the water had been taken off 600 volume parts of 0.5~ aqueous potassium hydroxide solution were introduced into the reactor and the deproteinlzation was carried out at a temperature of 50C for 4 h using a flow rate of 4580 volume parts per 1 weight part of shells and 1 hour. Next the alkaline solution containing proteins with a red colour, d~ = 1.112 g/cm3, pH = 12.06, was taken off from the reactor, and immediatel~i~ thereafter 500 volume parts of 60%
aqueous potassium hydroxide solution were introduced obtaining a 57.5% aqueous potassium hydroxide solution - as a result. Deacetylation was carried on at a temperature of 130C for 3 h. The alkaline solution was next taken off from the reactor and the product obtained was purified and dried at a temperature of 80C.
4.5 weight parts of chitosan with light red colour characterized by deacetylation degree of 75%, ash , contents of 0.35 wt%, nitrogen contes of 7.4 wt%, WRV
~ of 115% and a good solubility in 4% acetic acid - solution was obtained. IR studies showed the absorption band at the frequency of 1570 cm~1 characteristic of ~.
amine groups.
A prolongated deacetylation realized in the above conditions for the next 14 h allowed to obtain 4 weight parts of chitosan with a light red colour characterized by WRV of 120%, deacetylation degree of 92.5~, ash contents of 0.32 wt%, nitrogen contents of 7.9 wt% and a very good solubility in 4% aqueous acetic acid solution.
;' ' ', .
.
. .
studies showed the absorption band at the frequency of 1560 cm~1 characteristic of amine groups.
Exam~le 5 32.5 weight parts of milled crab shells characterized by nitrogen contents of 0.7 wt~, and 800 volume parts of 5~ aqueous hydrochloric acid solution were introduced into the reactor presented in Fig. 2.
Demineralization at a temperature of 70 for 90 minutes using a flow rate of 1580 volume parts per l weight part of shells and 1 hour was carried out, whereafter the acid solution was taken off and the residues were continuously washed by water with a flow rate of 5050 WO91/05808 PCT/Fl90/00247 ~o~ume parts per 1 weight part of shPlls and 1 hour.
After the water had been taken off 600 volume parts of 0.5~ aqueous potassium hydroxide solution were introduced into the reactor and the deproteinlzation was carried out at a temperature of 50C for 4 h using a flow rate of 4580 volume parts per 1 weight part of shells and 1 hour. Next the alkaline solution containing proteins with a red colour, d~ = 1.112 g/cm3, pH = 12.06, was taken off from the reactor, and immediatel~i~ thereafter 500 volume parts of 60%
aqueous potassium hydroxide solution were introduced obtaining a 57.5% aqueous potassium hydroxide solution - as a result. Deacetylation was carried on at a temperature of 130C for 3 h. The alkaline solution was next taken off from the reactor and the product obtained was purified and dried at a temperature of 80C.
4.5 weight parts of chitosan with light red colour characterized by deacetylation degree of 75%, ash , contents of 0.35 wt%, nitrogen contes of 7.4 wt%, WRV
~ of 115% and a good solubility in 4% acetic acid - solution was obtained. IR studies showed the absorption band at the frequency of 1570 cm~1 characteristic of ~.
amine groups.
A prolongated deacetylation realized in the above conditions for the next 14 h allowed to obtain 4 weight parts of chitosan with a light red colour characterized by WRV of 120%, deacetylation degree of 92.5~, ash contents of 0.32 wt%, nitrogen contents of 7.9 wt% and a very good solubility in 4% aqueous acetic acid solution.
;' ' ', .
.
. .
Claims (3)
1. Method of manufacture of chitosan and other products, such as chitin and proteins, from the shells of organisms, especially marine organisms, as a result of the reaction stages of deproteinization by alkaline solutions, demineralization by acidic solutions and deacetylation by concentrated alkaline solutions, the method comprising at least two successive stages of said three stages, characterized in that the shells of organisms, especially marine organisms, such as crabs or shrimps, are placed in a space in a reactor limited by a wall pervious to reaction liquids but retaining said shells of organisms, whereafter they are subjected to a continuous action of reaction liquids, especially in a recirculation system, flowing through the reactor and said space, and that after every reaction stage the solid product obtained is optionally washed by water using a continuous flow of water through the reactor to remove the residual reaction liquids, whereafter the solid end product is optionally dried, preferably in an air flow at a temperature of 40-100°C.
2. The method as claimed in claim 1, characterized in that the deproteinization is carried out by the use of alkaline solutions, especially aqueous alkaline metal hydroxide solutions or their salts, such as sodium hydroxide or sodium carbonate, at a concentration of 0.1-10 wt% at a tempreature of not lower than 10°C for a period of time necessary to complete the removal of proteins, the demineralization is carried out before or after deproteinization, using aqueous acid solutions, especially inorganic acids such as hydrochloric or sulfuric at a concentration of 0.1-20 wt% for a time necessary to dissolve the inorganic compounds such as calcium and WO91/05808 PCT/Fl90/00247 magnesium derivatives, at a temperature not lower than 10°C, especially 20-100°C, whereas the deacetylation is carried out using concentrated aqueous alkaline metal hydroxide solutions or their salts at a concentration of 20-60 wt% and for a time ranging from 30 minutes to 24 hours at a temperature of 60-140°C.
3. The method as claimed in claims 1 or 2, characterized in that the proteins are separated from the alkaline deproteinizing solutions by reduction of the pH of the solution to a level of pH in the range of 3-6 by an organic or inorganic acid solution, such as acetic, hydrochloric or sulfuric acid, especially at a concentration of 1-10 wt%, whereafter the chitin obtained after demineralization is purified and optionally dried.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI894989 | 1989-10-20 | ||
| FI894989A FI86068C (en) | 1989-10-20 | 1989-10-20 | Process for the production of chitosan and other products from shells of organisms, in particular from shells of marine organisms |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2067788A1 true CA2067788A1 (en) | 1991-04-21 |
Family
ID=8529194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002067788A Abandoned CA2067788A1 (en) | 1989-10-20 | 1990-10-19 | Method for manufacture of chitosan and other products from shells of organisms, especially marine organisms |
Country Status (4)
| Country | Link |
|---|---|
| CA (1) | CA2067788A1 (en) |
| FI (1) | FI86068C (en) |
| NO (1) | NO302661B1 (en) |
| WO (1) | WO1991005808A1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4442987C2 (en) * | 1994-12-02 | 1997-04-17 | Henkel Kgaa | Cationic chitin breakdown products |
| DE19503465A1 (en) * | 1995-02-03 | 1996-08-08 | Henkel Kgaa | Process for the production of low-viscosity cationic biopolymers |
| DE19510312C2 (en) * | 1995-03-22 | 2000-06-15 | Cognis Deutschland Gmbh | Polymeric dyes |
| DE19524125C2 (en) | 1995-07-03 | 2001-01-04 | Cognis Deutschland Gmbh | Hair cosmetic preparations |
| DE19537001C2 (en) * | 1995-08-28 | 1997-12-11 | Henkel Kgaa | Hair sprays |
| DE19542141C2 (en) | 1995-11-11 | 1998-07-30 | Henkel Kgaa | Cosmetic and / or pharmaceutical emulsions |
| DE19604180C2 (en) * | 1996-02-06 | 1997-12-18 | Henkel Kgaa | Process for the production of biopolymers with improved surfactant solubility |
| US5968488A (en) * | 1996-10-21 | 1999-10-19 | Henkel Kommanditgesellschaft Auf Aktien | Deodorizing preparations containing cationic biopolymers, aluminum hydrochlorate and esterase inhibitors |
| NO982673L (en) * | 1998-06-10 | 1999-12-13 | Bioeffect As | Preparation of chitosan |
| DE19849189A1 (en) * | 1998-10-26 | 2000-05-04 | Henkel Kgaa | Process for extracting natural substances by extraction and for producing chitin or chitosan |
| DE10014997A1 (en) * | 2000-03-25 | 2001-09-27 | Cognis Deutschland Gmbh | Production of chitin comprises demineralizing and deproteinizing a chitin-containing material in the presence of a biodegradable complexing agent and a protease |
| JP2011515541A (en) * | 2008-03-19 | 2011-05-19 | アグラテック インターナショナル インコーポレイテッド | Chitosan generation method |
| WO2018122700A1 (en) * | 2016-12-30 | 2018-07-05 | Tubitak | Production method of environmentally friendly chitosan from acrididae, tenebrionidae and gammaridae families |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2040879A (en) * | 1934-06-21 | 1936-05-19 | Du Pont | Substantially undegraded deacetylated chitin and process for producing the same |
| US3862122A (en) * | 1972-02-16 | 1975-01-21 | Quintin P Peniston | Method of recovering chitosan and other by-products from shellfish waste and the like |
| US4199496A (en) * | 1974-09-05 | 1980-04-22 | Johnson Edwin L | Process for the recovery of chemicals from the shells of crustacea |
| JPS5359700A (en) * | 1976-11-10 | 1978-05-29 | Nihon Tennen Gas Kogyo Co Ltd | Production of chitosan |
| JPS62179503A (en) * | 1986-02-03 | 1987-08-06 | Lion Corp | Production of chitosan |
-
1989
- 1989-10-20 FI FI894989A patent/FI86068C/en not_active IP Right Cessation
-
1990
- 1990-10-19 WO PCT/FI1990/000247 patent/WO1991005808A1/en active Application Filing
- 1990-10-19 CA CA002067788A patent/CA2067788A1/en not_active Abandoned
-
1992
- 1992-04-13 NO NO921464A patent/NO302661B1/en not_active IP Right Cessation
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| Publication number | Publication date |
|---|---|
| NO302661B1 (en) | 1998-04-06 |
| FI86068C (en) | 1992-07-10 |
| FI894989A0 (en) | 1989-10-20 |
| FI86068B (en) | 1992-03-31 |
| NO921464D0 (en) | 1992-04-13 |
| NO921464L (en) | 1992-04-15 |
| WO1991005808A1 (en) | 1991-05-02 |
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