DK157452B - PROCEDURE FOR THE EXTRACTION OF CHITIN FROM CHITINE SOURCES, WHICH IT IS TOGETHER WITH OR CONNECTED TO PROTEIN SUBSTANCES - Google Patents
PROCEDURE FOR THE EXTRACTION OF CHITIN FROM CHITINE SOURCES, WHICH IT IS TOGETHER WITH OR CONNECTED TO PROTEIN SUBSTANCES Download PDFInfo
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- 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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Description
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Chitin er et nitrogenholdigt, polymert carbonhy-drat, som forekommer udbredt i naturen, især i det eksterne skelet hos insekter, skaldyr og bløddyr, men også i visse svampe.Chitin is a nitrogenous polymeric carbohydrate which is widespread in nature, especially in the external skeleton of insects, shellfish and molluscs, but also in certain fungi.
5 Chitin samt stoffet chitosan, som kan fremstilles ved deacetylering af chitin med stærke baser, har en række industrielle anvendelsesmuligheder, f.eks. som fortykkelsesmidler, geleringsmidler, filmdannende midler, ionbyttere og flokkulenter samt som tungmetalbin-10 dende midler, suturmaterialer og som sårhelende midler.Chitin as well as the substance chitosan, which can be produced by deacetylation of strong base chitin, have a number of industrial applications, e.g. as thickeners, gelling agents, film-forming agents, ion exchangers and flocculants, and as heavy metal binding agents, suture materials and as wound healing agents.
I de vigtigste chitinkilder, såsom skaller fra rejer, krill og krabber, forekommer chitin sammen med, og til dels bundet til, proteinstoffer. Derudover indeholder de pågældende skaller en betydelig mængde mine-15 ralstof, navnlig calciumcarbonat.In the major sources of chitin, such as shells from shrimp, krill and crabs, chitin occurs along with, and partly bound to, protein substances. In addition, the shells in question contain a significant amount of mineral matter, in particular calcium carbonate.
Endvidere indeholder mange chitinkilder farvestoffet astaxanthin og derivater deraf, som har stor værdi som følge af dets anvendelighed i foder til laksefisk .Furthermore, many chitin sources contain the dye astaxanthin and its derivatives which are of great value due to its utility in feed for salmonids.
20 Der har været gjort adskillige forsøg på at ud vikle metoder til fremstilling af chitin eller chitosan ud fra skaller af marine skaldyr. Sådanne skaller må for nærværende betragtes som den væsentligste chitinkil-de, og fremgangsmåden ifølge opfindelsen beskrives i det 25 følgende i forbindelse med oparbejdning af disse, specielt skaller af rejer og krill, men den er generelt anvendelig til alle chitinkilder, hvorfra der skal fjernes protein.Several attempts have been made to develop methods for producing chitin or chitosan from marine shellfish shells. Such shells are presently considered to be the major source of chitin, and the process of the invention is described below in connection with their processing, especially shells of shrimp and krill, but it is generally applicable to all chitin sources from which protein is to be removed. .
Fælles for de foreslåede metoder er, at skaller-30 nes kalkindhold fjernes ved behandling med en syre, medens proteinet har været foreslået fjernet ved behandling med stærk natriumhydroxidopløsning eller med enzympræparater (pepsin fra svin eller fisk). Endvidere har det været foreslået at nedbryde proteinen med proteolyt-35 tiske bakterier.Common to the proposed methods is that the lime content of the shells is removed by treatment with an acid, while the protein has been proposed to be removed by treatment with strong sodium hydroxide solution or with enzyme preparations (pepsin from pigs or fish). Furthermore, it has been proposed to break down the protein with proteolytic bacteria.
Proteinfjernelse med natriumhydroxid eller andre stærke baser har den ulempe, at en væsentlig del afProtein removal with sodium hydroxide or other strong bases has the disadvantage that a substantial part of
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2 skallernes astaxanthinindhold går tabt og endvidere hydrolyseres en del af chitinen til chitosan, således at der ikke opnås et rent produkt.2 astaxanthin content of the shells is lost and further part of the chitin is hydrolyzed to chitosan so that no pure product is obtained.
Anvendelse af proteolytiske bakterier medfører en 5 kompliceret arbejdsgang, og proteinfjernelse med enzympræparater har ikke ført til en tilstrækkelig effektiv proteinopløsning og har givet et relativt dårligt asta-xanthinudbytte.The use of proteolytic bacteria entails a complicated process and protein removal with enzyme preparations has not led to a sufficiently effective protein solution and has produced a relatively poor asta-xanthine yield.
Et væsentligt bedre astaxanthinudbytte er opnået 10 ved at behandle rejeskaller med en ensilage, fremstillet ved behandling af torskeindvolde uden lever med myresyre og propionsyre til en pH-værdi i blandingen på 4,1 - 4,5, idet pH-værdien ved behandlingen af rejeskallerne blev holdt på 2,5 - 3,0. Denne behandling gav en effek-15 tiv proteinopløsning, men samtidig blev en betydelig del af chitinen nedbrudt, hvorfor udbyttet heraf var utilfredsstillende .Significantly better astaxanthin yield is obtained by treating shrimp shells with a silage prepared by treating cod liver without liver with formic acid and propionic acid to a pH of the mixture of 4.1 - 4.5, the pH of the treatment of the shrimp shells. was held at 2.5 - 3.0. This treatment yielded an effective protein solution, but at the same time a considerable part of the chitin was degraded, and the yield thereof was unsatisfactory.
For at separere astaxanthinen har man ekstraheret denne med en olie, såsom sojaolie.To separate the astaxanthin, it has been extracted with an oil such as soybean oil.
20 Det har nu vist sig, at man ved at behandle fi skeindvolde, fortrinsvis findelte, med en syre til opnåelse af en pH-værdi i området fra 1,2 - 2,5, kan påvirke indvoldenes enzymaktivitet såedes, at den chitin-nedbrydende aktivitet vidtgående undertrykkes samtidig 25 med, at den proteolytiske aktivitet kun svækkes i mindre grad. Det har endvidere vist sig, at denne svækkelse af de chitinnedbrydende enzymers aktivitet i betydelig grad er irreversibel, hvis indvoldene holdes ved den lave pH-værdi i længere tid, således som tilfældet er, når de 30 ensileres. Dette betyder, at man ved anvendelse af en ensilage af fiskeindvolde med en pH-værdi på 1,2 - 2,5 kan tillade en forøgelse af pH-værdien op til 4 under behandlingen af reje- eller krillskallerne og derved få en god proteolyse uden væsentlig nedbrydning af chiti-3 5 nen.It has now been found that by treating the viscera, preferably finely divided, with an acid to obtain a pH in the range of 1.2 - 2.5, the enzyme activity of the viscera can be affected so that the chitin-degrading activity is extensively suppressed at the same time as the proteolytic activity is only attenuated to a lesser extent. Furthermore, it has been found that this impairment of the activity of the chitin-degrading enzymes is significantly irreversible if the entrails are kept at the low pH for a longer period, as is the case when they are ensiled. This means that by using a silage of fish entrails with a pH of 1.2 - 2.5, an increase in the pH of up to 4 can be allowed during the treatment of the shrimp or krill shells and thereby obtain a good proteolysis without significant degradation of the chiti-3 5.
I tilfælde af, at der i stedet for ensilage an-In the event that instead of silage,
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3 vendes friske fiskeindvolde, eller hvis ensilagen har været fremstillet ved pH-værdien større end 2,5, vil man derimod gennemføre proteolysen ved en pH-værdi på 1,2 - 2,5.In the case of fresh fish entrails, if the silage has been prepared at a pH greater than 2.5, the proteolysis will be carried out at a pH of 1.2 - 2.5.
5 Opfindelsen angår således en fremgangsmåde til udvinding af chitin fra chitinkilder, hvori stoffet foreligger sammen med eller bundet til proteinstoffer og eventuelt sammen med astaxanthin, ved demineralisering med en syre og behandling med midler til fjernelse af 10 protein og den eventuelt foreliggende astaxanthin, hvilken fremgangsmåde er ejendommelig ved, at man: a) fremstiller en vandig suspension af den eventuelt hakkede chitinkilde og fiskeindvolde eller fiskeindvoldsensilage samt eventuelt en olie eller et 15 olieafgivende materiale, idet der drages omsorg for, at fiskeindvoldene eller ensilagen indvirker på chitinkilden ved en pH-værdi på 1,2 - 2,5, fortrinsvis 1,5 - 2,5, eller at der ved fremstilling af ensilagen er anvendt en sådan pH-værdi, i 20 hvilket tilfælde indvirkningen foretages ved en pH-værdi mellem 1,2 og 4, b) opvarmer suspensionen til en temperatur mellem 25 og 50°C i et tidsrum mellem nogle få timer og fire døgn, fortrinsvis lA - 3 døgn, og 25 c) separerer suspensionen til opnåelse af i det mindste (i) en vandig fase, som indeholder pro-teinhydrolysat i opløst form, og (ii) en fraktion, som indeholder chitinen i det væsentlige fri for proteiner og mineralstoffer, og (iii) 30 eventuelt en oliefraktion, som indeholder asta xanthin.The invention thus relates to a process for the extraction of chitin from chitin sources wherein the substance is present with or linked to protein substances and optionally together with astaxanthin, by demineralization with an acid and treatment with means for removing protein and the optionally available astaxanthin, which method is peculiar in that: a) preparing an aqueous suspension of the chopped source of chopped and viscous or viscous silage, and optionally an oil or oil-releasing material, taking care that the fish chew or silage acts on the chitin source at a pH of 1.2 - 2.5, preferably 1.5 - 2.5, or that such a pH is used in the preparation of the silage, in which case the effect is made at a pH between 1.2 and 4 b) heating the suspension to a temperature between 25 and 50 ° C for a period of a few hours to four days, preferably 1 to 3 days, and 25 c) separating the suspension to obtain at least (i) an aqueous phase containing protein hydrolyzate in dissolved form, and (ii) a fraction containing the chitin substantially free of proteins and minerals, and (iii) optionally an oil fraction containing asta xanthine.
Fortrinsvis foretager man mellem trin b) og c) en delvis neutralisation og en opvarmning af suspensionen til 80 - 95°C til inaktivering af dennes enzym- og mi-35 kroorganismeindhold og for at lette den påfølgende separering.Preferably, between steps b) and c) a partial neutralization and heating of the suspension is made to 80 - 95 ° C to inactivate its enzyme and microorganism content and to facilitate subsequent separation.
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4 Nævnte separering ved fremgangsmådens trin c) udføres hensigtsmæssigt under anvendelse af en dekantør, kombineret med en centrifugering. Den ved centrifugeringen opnåede slamfraktion, som indeholder chitinen, 5 vaskes gentagne gange og renses og tørres til opnåelse af et holdbart produkt. Ved en efterfølgende operation eller som alternativ til den nævnte tørring kan chitinen viderebehandles, f.eks. ved opvarmning med en stærk base til opnåelse af chitosan.Said separation at step c) of the process is conveniently carried out using a decanter combined with a centrifugation. The sludge fraction obtained by centrifugation containing the chitin is repeatedly washed and purified and dried to give a durable product. In a subsequent operation or as an alternative to said drying, the chitin may be further treated, e.g. by heating with a strong base to obtain chitosan.
10 Hvis den anvendte chitinkilde indeholder astaxan- thin, kan denne ekstraheres med en olie, fortrinsvis i forbindelse med den proteolytiske behandling, og man vil i så fald ved separeringen i trin c) foruden en vandig fraktion, som indeholder proteinhydrolysat og en slam-15 fraktion, som indeholder chitinen, opnå en oliefraktion, som indeholder den væsentlige mængde astaxanthin fra udgangsmaterialet. Denne oliefraktion vil sædvanligvis kunne afsættes uden opkoncentrering af den deri værende astaxanthin.If the chitin source used contains astaxanthin, it can be extracted with an oil, preferably in connection with the proteolytic treatment, and then in the separation in step c), in addition to an aqueous fraction containing protein hydrolyzate and a sludge, fraction containing the chitin obtains an oil fraction containing the substantial amount of astaxanthin from the starting material. This oil fraction can usually be deposited without concentrating the astaxanthin present therein.
20 Ved en foretrukken udførelsesform ekstraherer man astaxanthinen med en marin olie, som tilvejebringes ved at anvende fiskelever eller andre olieholdige dele af fisk, hvorfra olien frigøres under indvirkning af den proteolytiske aktivitet af den resterende del af indvol-25 dene, hvilken olie, som nævnt, separeres som en særlig fraktion i trin c).In a preferred embodiment, the astaxanthin is extracted with a marine oil, which is obtained by using fish liver or other oily portions of fish, from which the oil is released under the influence of the proteolytic activity of the remaining part of the viscera, as mentioned above. , is separated as a special fraction in step c).
Alternativt kan der tilføres en olie, som f.eks. sojaolie, men det vil ofte være mere økonomisk fordelagtigt at medtage fiskelever, såsom torskelever, eller an-30 dre olieholdige dele af fisk ved fremstilling af den ensilage, som benyttes ved fremgangsmåden ifølge opfindelsen eller at tilføre torskelever eller lignende ved fremstilling af suspensionen i trinnet a). I begge tilfælde vil fiskeindvoldenes proteolytiske enzymer be-35 virke en sådan nedbrydning af de olieholdige væv, at olien frigøres og senere-kan separeres i trinnet c).Alternatively, an oil may be added, e.g. soybean oil, but it will often be more economically advantageous to include fish liver, such as cod liver, or other oily portions of fish in the preparation of the silage used in the process of the invention or to feed cod liver or the like in preparing the suspension in the step. a). In either case, the proteolytic enzymes of the fish entrails will cause such degradation of the oily tissues that the oil is released and later separable in step c).
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Den ved separeringen opnåede vandige fase har et betydeligt indhold af proteinhydrolysat og kan efter eventuel neutralisation anvendes som komponent i husdyrfoder, fortrinsvis efter tørring.The aqueous phase obtained during the separation has a considerable content of protein hydrolyzate and can be used as a component in livestock feed, preferably after drying, after possible neutralization.
5 Det vil af ovenstående fremgå, at en udførelses form for fremgangsmåden er ejendommelig ved, at suspensionen i trin a) fremstilles under anvendelse af en af fiskeindvolde og uorganisk syre fremstillet ensilage med en pH-værdi på 1,2 - 2,5, fortrinsvis 1,5 - 2,5, idet 10 suspensionens pH indstilles til højst 4.It will be apparent from the foregoing that an embodiment of the process is peculiar in that the suspension of step a) is prepared using a silage and inorganic acid prepared silage having a pH of 1.2 - 2.5, preferably 1.5 to 2.5, adjusting the pH of the suspension to a maximum of 4.
Ved en anden udførelsesform for fremgangsmåden fremstilles suspensionen i trin a) under anvendelse af friske fiskeindvolde, og dens pH-værdi indstilles til 1,2 - 2,5, fortrinsvis 1,5 - 2,5.In another embodiment of the method, the suspension is prepared in step a) using fresh fish entrails and its pH is adjusted to 1.2 - 2.5, preferably 1.5 - 2.5.
15 Når der anvendes rejeskaller som chitinkilde, vil disse blive opsamlet i et rejepilleri, hvor de sædvanligvis presses til et tørstofindhold på ca. 50%. Som følge af den dårlige holdbarhed vil man sædvanligvis konservere rejeskallerne ved tilsætning af en stærk, 20 uorganisk syre til en pH-værdi mindre end 3, og herved sker der samtidig en demineralisering af skallerne.When shrimp shells are used as a source of chitin, these will be collected in a shrimp pellet, where they are usually pressed to a dry matter content of approx. 50%. Due to the poor shelf life, the shrimp shells will usually be preserved by the addition of a strong, 20 inorganic acid to a pH less than 3, thereby simultaneously demineralizing the shells.
Hvor råmaterialet er rå rejeskaller, konserveres det fortrinsvis ved pH 1,2 - 2,5.Where the raw material is raw shrimp shells, it is preferably preserved at pH 1.2 - 2.5.
Da enzymaktiviteten af fiskeindvolde og ensilage, 25 fremstillet herudaf, varierer meget stærkt, bl.a. afhængigt af fiskens art og fodertilstand samt årstiden og ensilagens opbevaringstid og -temperatur, kan der ikke angives eksakte grænser for hvilke forhold mellem chitinkilde og fiskeindvolde eller ensilage, der skal an-30 vendes. Med rejeskaller er gode resultater opnået med et vægtforhold på ca. 1:2, idet mængden af rejeskaller er beregnet ud fra et presset materiale med ca. 50%'s tørstof.As the enzyme activity of fish viscera and silage, produced therefrom, varies greatly, i. Depending on the nature and condition of the fish, as well as the time of year and the storage time and temperature of the silage, no exact limits can be specified for the ratio of chitin source to fish entrails or silage to be used. With shrimp shells good results are obtained with a weight ratio of approx. 1: 2, the amount of shrimp shells calculated from a pressed material of approx. 50% dry matter.
Da navnlig astaxanthinen er meget følsom for oxi-35 dation, vil man sædvanligvis sørge for, at der er anti-oxidanter til stede under processen, hvilke antioxidan-In particular, since the astaxanthin is very sensitive to oxidation, anti-oxidants will usually be present during the process which
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6 ter fortrinsvis indføres på et så tidligt stade i processen som muligt, dvs. ved den eventuelle forudgående konservering af chitinkilden med syre, og ved den eventuelle forudgående oparbejdning af fiskeindvoldene til 5 ensilage. Ved anvendelse af friske ud-gangsmaterialer tilsættes antioxidanter ved oparbejdning af suspensionen i trin a). Som antioxidanter kan anvendes stoffer, som er sædvanlige til sådanne formål, såsom butylhydroxyani- sol.6ters are preferably introduced at the earliest stage in the process, i.e. by the possible prior preservation of the chitin source with acid, and by the possible prior processing of the fish entrails into 5 silages. Using fresh starting materials, antioxidants are added by working up the suspension in step a). Substances which are customary for such purposes as butyl hydroxyanisol may be used as antioxidants.
10 For at opnå en større renhed af den som slamfrak tion ved separeringen opnåede chitin, kan det være hensigtsmæssigt ved oparbejdning af suspensionen i trin a) at benytte en fiskeindvoldsensilage, som forud er befriet for slam.In order to obtain a higher purity of the chitin obtained as a sludge fraction during the separation, it may be appropriate to work up the suspension in step a) to use a fish entrained silage which has been previously freed of sludge.
15 Som syre ved de eventuelle forudgående ensilerin- ger eller konserveringer af f.eks. reje- eller krill-skallerne samt til opnåelse af den ønskede pH-værdi for suspensionen, benyttes saltsyre eller svovlsyre eller anden stærk syre.15 As an acid in the event of any prior silage or preservation of e.g. the shrimp or krill shells and to obtain the desired pH of the suspension, hydrochloric or sulfuric or other strong acid is used.
2020
Fremgangsmåden ifølge opfindelen illustreres nærmere ved hjælp af nedenstående udførelseseksempel.The method according to the invention is further illustrated by the following example.
EKSEMPELEXAMPLE
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Seks portioner fiskeindvoldsensilage blev fremstillet ved til hver portion at anvende ca. 500 kg. lever og indvolde fra torsk, 15 1 50 vægt%'s svovlsyre og 5 g butylhydroxyanisol (som antioxidant). Svovlsyren 30 blev tilsat, medens lever og indvolde blev blandet intensivt i et 1000 1 kar under anvendelse af et neddykket blandeapparat. Intensivblandingen blev fortsat i 15 minutter, hvorpå blandingen ved pumpning blev overført til en tank, hvori den blev forenet med de øvrige fem 35 portioner, fremstillet på samme måde.Six portions of fish viscous silage were prepared by using approximately one portion for each serving. 500 kg. liver and viscera from cod, 15 1 50% by weight of sulfuric acid and 5 g of butyl hydroxyanisole (as antioxidant). Sulfuric acid 30 was added while the liver and viscera were mixed intensively in a 1000 L vessel using a submerged mixer. The intensive mixture was continued for 15 minutes, after which the mixture was pumped to a tank in which it was combined with the other five portions prepared in the same manner.
Blandingens pH-værdi var ca. 2,0.The pH of the mixture was approx. 2.0.
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Den således fremstillede ensilage blev opbevaret i tanken i to døgn, medens den intermitterende blev holdt i bevægelse ved ompumpning.The silage thus produced was stored in the tank for two days while the intermittent was kept moving by pumping.
Til fjernelse af partikelformet materiale og slam 5 blev ensilagen passeret gennem en centrifugaldekantør og pumpet til en 5 m3 kugletank.To remove particulate matter and sludge 5, the silage was passed through a centrifugal box and pumped to a 5 m3 ball tank.
På dette stadium havde lever- og indvoldsensilagen (ca. 3000 kg) følgende omtrentlige sammensætning: 10 Olie 20 vægt% Tørstof, forskelligt fra fedt 11 vægt%At this stage, the liver and viscera silage (about 3000 kg) had the following approximate composition: 10 Oil 20% by weight Dry matter, different from fat 11% by weight
Protein 8 vægt%Protein 8% by weight
Aske 2 vægt%.Ash 2% by weight.
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De skaller, som fremkommer som affald fra en re-jepillemaskine, har følgende omtrentlige sammensætning (efter afdræning af vand): 20 Tørstof 20 vægt%The shells resulting from waste from a shredder have the following approximate composition (after draining water): 20 Solids 20% by weight
Protein 5 vægt%Protein 5% by weight
Chitin 5 vægt%Chitin 5% by weight
Fedt 0,5 vægt%Fat 0.5% by weight
Aske 6,5 vægt% 25 Astaxanthin 50 ppm.Ash 6.5% by weight 25 Astaxanthin 50 ppm.
Portioner på hver 250 kg rejeskaller blev omrørt med 600 1 vand i et 1000 1 kar, og der blev tilsat 11 1 96%'s svovlsyre og 1 g butylhydroxyanisol. pH-værdien 30 var ca. 2,0.Servings of each 250 kg of shrimp shells were stirred with 600 L of water in a 1000 L vessel and 11 1 96% sulfuric acid and 1 g of butyl hydroxyanisole were added. The pH 30 was approx. 2.0.
Efter at en tilstrækkelig mængde rejeskaller var blevet ensileret på denne måde, blev de pumpet til en snekkepresse til frembringelse af 1500 kg pressekage med ca. 40%'s tørstof. Denne pressekage havde følgende sam-35 mensætning.After a sufficient amount of shrimp shells had been silenced in this way, they were pumped to a worm press to produce 1500 kg of press cake with approx. 40% dry matter. This press cake had the following composition.
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8 Tørstof 40 vægt%8 Solids 40% by weight
Protein 15 vægt%Protein 15% by weight
Chitin 15 vægt%Chitin 15% by weight
Fedt 1,5 vægt% 5 Aske 6 vægt%Fat 1.5% by weight 5 Ash 6% by weight
Astaxanthin 150 ppm.Astaxanthin 150 ppm.
En væsentlig del af det calciumsulfat, som blev dannet ved omsætning mellem svovlsyren og calciumcarbo-10 nat i skallerne, blev fjernet sammen med pressevandet.A substantial portion of the calcium sulfate formed by reaction between the sulfuric acid and calcium carbonate in the shells was removed together with the press water.
Dette pressevand kan anvendes til behandling af en yderligere mængde rejeskaller til formindskelse af forbruget af svovlsyre og for at undgå, at den sure væske skal udledes i milieuet.This pressurized water can be used to treat an additional amount of shrimp shells to reduce the consumption of sulfuric acid and to prevent the acidic liquid from being discharged into the environment.
15 Den opnåede pressekage af syrebehandlede rejes kaller blev indført i kugletanken med lever- og indvoldsensilagen, hvori skallerne blev opslæmmet. Den resulterende suspension havde en viskositet på 2-3000 mPa's, pH-værdien var ca. 2.15 The obtained cake of acid-treated shrimp calls was introduced into the ball tank with the liver and viscera silage, in which the shells were slurried. The resulting suspension had a viscosity of 2-3000 mPa 2nd
20 Blandingen blev opvarmet til 35°C ved hjælp af en varmespole, gennem hvilken der blev cirkuleret vand ved 45°C. Blandingen blev holdt i bevægelse ved pumpning.The mixture was heated to 35 ° C by means of a heating coil through which water was circulated at 45 ° C. The mixture was kept moving by pumping.
Efter i to døgn at have været opvarmet til 35°C og holdt i bevægelse, blev suspensionen opvarmet til 25 80°C med damp og derpå pumpet til snekkepressen, hvor olie og en vandig opløsning af hydrolyseret protein blev adskilt fra den rå chitin. Den flydende fase blev behandlet i en dekantørcentrifuge til fjernelse af slam og derpå adskilt ved centrifugering i en oliefraktion og en 30 fraktion af vandig proteinhydrolysat.After being heated to 35 ° C for two days and kept in motion, the suspension was heated to 25 ° C with steam and then pumped to the screw press where oil and an aqueous solution of hydrolyzed protein were separated from the crude chitin. The liquid phase was treated in a decanter centrifuge to remove sludge and then separated by centrifugation in an oil fraction and a fraction of aqueous protein hydrolyzate.
Olien indeholdt ca. 55% af den astaxanthin, som oprindeligt var til stede i rejeskallerne, svarende til ca. 200 ppm astaxanthin i olien. Olien kan anvendes som sådan til fremstilling af foder til laks og beslægtede 35 fisk, hvis kød ønskes bibragt en rødlig farve.The oil contained approx. 55% of the astaxanthin originally present in the shrimp shells, corresponding to approx. 200 ppm astaxanthin in the oil. The oil can be used as such for the preparation of feed for salmon and related fish whose meat is desired to have a reddish color.
Proteinhydrolysatet blev inddampet og tørret til 9The protein hydrolyzate was evaporated and dried to 9
DK 157452 BDK 157452 B
opnåelse af et produkt, som var egnet som tilsætning til foder til kvæg og fjerkræ.obtaining a product suitable for addition to feed for cattle and poultry.
Pressekagen, som omfattede rejeskallernes chitin, blev suspenderet i 2000 1 vand ved 80°C, og suspensionen 5 ompumpet i 15 miutter. Suspensionen blev derpå pumpet til pressen, og den herved opnåede væskefase blev ved hjælp af en dekantør og en centrifuge adskilt til udvinding af en yderligere mængde astaxantinholdig olie.The press cake, which included the shrimp shells chitin, was suspended in 2000 l of water at 80 ° C and the suspension 5 re-pumped for 15 minutes. The suspension was then pumped to the press and the resulting liquid phase separated by means of a decanter and centrifuge to recover an additional amount of astaxanthin-containing oil.
Den vandige fase fra denne adskillelse blev kasseret.The aqueous phase from this separation was discarded.
10 Chitinpressekagen blev suspenderet en gang yder ligere i 2000 1 vand ved 80°C, og der blev tilsat 20 kg natriumcarbonat. Suspensionen blev omrørt, og chltimen atter isoleret ved hjælp af snekkepressen.The chitin squeeze cake was suspended once more in 2000 liters of water at 80 ° C and 20 kg of sodium carbonate was added. The suspension was stirred and the chime was again isolated by the screw press.
Chitinen blev skyllet en gang yderligere på lig-15 nende måde under anvendelse af vand uden natriumcarbonat, og derpå blev skylningen gentaget under tilsætning af 10 1 30 vægt%'s saltsyre.The chitin was rinsed once more in a similar manner using water without sodium carbonate, and then rinsed again with the addition of 10 1 30% by weight of hydrochloric acid.
Den opnåede chitinkage blev til slut vasket med 2000 1 rent vand, ligeledes ved 80°C og atter presset.The resulting chitin cake was finally washed with 2000 liters of pure water, also at 80 ° C and pressed again.
20 Den resulterende kage af chitin blev tørret under anvendelse af varm luft til opnåelse af 225 kg chitin med følgende data:The resulting chitin cake was dried using hot air to obtain 225 kg of chitin with the following data:
Farve: hvid med en svag rødlig tone 25 Protein <0,5 vægt%Color: white with a slight reddish tone 25 Protein <0.5% by weight
Olie <0,1 vægt%Oil <0.1% by weight
Aske <0,5 vægt%.Ash <0.5% by weight.
Hvis der ønskes et produkt med ekstremt lav aske- 30 indhold, kan den sidste vaskningsproces udføres med partielt demineraliseret vand.If a product with extremely low ash content is desired, the final washing process can be carried out with partially demineralized water.
3535
Claims (8)
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK166285A DK157452C (en) | 1985-04-12 | 1985-04-12 | PROCEDURE FOR THE EXTRACTION OF CHITIN FROM CHITINE SOURCES, WHICH IT IS TOGETHER WITH OR CONNECTED TO PROTEIN SUBSTANCES |
| ES553767A ES8706170A1 (en) | 1985-04-12 | 1986-04-08 | A process for recovering chitin from materials in which chitin occurs together with or connected to proteinaceous substances. |
| IS3090A IS1458B6 (en) | 1985-04-12 | 1986-04-08 | A method of working and purifying chitin |
| AU56946/86A AU5694686A (en) | 1985-04-12 | 1986-04-09 | A process for recovering chitin from materials in which chitin occurs together with or connected to proteinaceous substances |
| EP86902350A EP0217887A1 (en) | 1985-04-12 | 1986-04-09 | A process for recovering chitin from materials in which chitin occurs together with or connected to proteinaceous substances |
| PCT/DK1986/000034 WO1986006082A1 (en) | 1985-04-12 | 1986-04-09 | A process for recovering chitin from materials in which chitin occurs together with or connected to proteinaceous substances |
| IN284/CAL/86A IN165452B (en) | 1985-04-12 | 1986-04-11 | |
| PT82378A PT82378B (en) | 1985-04-12 | 1986-04-11 | Process for recovering chitin from materials in which chitin occurs together with or connected to proteinaceous substances |
| AR86303626A AR242592A1 (en) | 1985-04-12 | 1986-04-11 | A process for recovering chitin from materials in which chitin occurs together with or connected to proteinaceous substances |
| NO865015A NO165966C (en) | 1985-04-12 | 1986-12-11 | PROCEDURE FOR THE RECOVERY OF CHITIN FROM MATERIALS WHORCHITIN OPERATES WITH, OR IN CONNECTION WITH, PROTEIN SUBSTANCES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DK166285 | 1985-04-12 | ||
| DK166285A DK157452C (en) | 1985-04-12 | 1985-04-12 | PROCEDURE FOR THE EXTRACTION OF CHITIN FROM CHITINE SOURCES, WHICH IT IS TOGETHER WITH OR CONNECTED TO PROTEIN SUBSTANCES |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| DK166285D0 DK166285D0 (en) | 1985-04-12 |
| DK166285A DK166285A (en) | 1986-10-13 |
| DK157452B true DK157452B (en) | 1990-01-08 |
| DK157452C DK157452C (en) | 1990-05-21 |
Family
ID=8107002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK166285A DK157452C (en) | 1985-04-12 | 1985-04-12 | PROCEDURE FOR THE EXTRACTION OF CHITIN FROM CHITINE SOURCES, WHICH IT IS TOGETHER WITH OR CONNECTED TO PROTEIN SUBSTANCES |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0217887A1 (en) |
| AR (1) | AR242592A1 (en) |
| AU (1) | AU5694686A (en) |
| DK (1) | DK157452C (en) |
| ES (1) | ES8706170A1 (en) |
| IN (1) | IN165452B (en) |
| IS (1) | IS1458B6 (en) |
| NO (1) | NO165966C (en) |
| PT (1) | PT82378B (en) |
| WO (1) | WO1986006082A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO176323C (en) * | 1988-11-18 | 1995-03-15 | Mikalsen Ester | Process for Extraction of Astaxanthin, Related Carotenoids and Astaxanthin Esters from Krill, Shrimp and Other Crustaceans |
| FR2701029B1 (en) * | 1993-01-20 | 1995-04-07 | Aber Technologies | Process for obtaining chitin and / 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 |
| US6632941B2 (en) | 2001-09-14 | 2003-10-14 | James Wooten | Method of extracting chitin from the shells of exoskeletal animals |
| JP5509444B2 (en) | 2005-08-15 | 2014-06-04 | ファレス ファーマシューティカル リサーチ エヌ．ブイ． | Crystalline form of astaxanthin |
| WO2007128574A1 (en) | 2006-05-10 | 2007-11-15 | Dsm Ip Assets B.V. | Process for the preparation of astaxanthin |
| US8697138B2 (en) | 2007-03-28 | 2014-04-15 | Aker Biomarine As | Methods of using krill oil to treat risk factors for cardiovascular, metabolic, and inflammatory disorders |
| ES2415684T3 (en) | 2007-03-28 | 2013-07-26 | Aker Biomarine As | Biologically effective krill oil compositions |
| AU2012244229B2 (en) * | 2007-08-29 | 2013-11-21 | Aker Biomarine Antarctic As | A new method for making krill meal |
| KR101343290B1 (en) * | 2007-08-29 | 2013-12-18 | 에이커 바이오마린 에이에스 | A new method for making krill meal |
| RU2548178C2 (en) | 2008-03-19 | 2015-04-20 | Агратек Интернэшнл, Инк. | Method of obtaining chitosan |
| US8372812B2 (en) | 2009-02-26 | 2013-02-12 | Aker Biomarine Asa | Phospholipid and protein tablets |
| DE102009028980A1 (en) | 2009-08-28 | 2011-03-03 | Technische Universität Dresden | Two- or three-dimensional purified Chitingerüst of horn sponges, process for its preparation and use |
| KR101616446B1 (en) | 2009-10-30 | 2016-04-28 | 샤로스 리미티드 | Solvent-free process for obtaining phospholipids and neutral enriched krill oils |
| FR2975706B1 (en) * | 2011-05-26 | 2017-07-21 | Ifremer (Institut Francais De Rech Pour L'exploitation De La Mer) | EXTRACTION OF CHITINS IN ONE STEP BY ENZYMATIC HYDROLYSIS IN ACID |
| AU2014203179C1 (en) | 2013-06-14 | 2017-05-04 | Aker Biomarine Antarctic As | Lipid extraction processes |
| GB201400431D0 (en) | 2014-01-10 | 2014-02-26 | Aker Biomarine As | Phospholipid compositions and their preparation |
| EP3256003B1 (en) | 2015-02-11 | 2022-11-09 | Aker Biomarine Antarctic AS | Lipid extraction processes |
| NZ735362A (en) | 2015-02-11 | 2019-01-25 | Aker Biomarine Antarctic As | Lipid compositions |
| CN108559765A (en) * | 2017-12-28 | 2018-09-21 | 南京工业大学 | A kind of method that biological enzyme extracts N-acetylglucosamine and astaxanthin from cray shell |
| CN112375161B (en) * | 2020-12-13 | 2022-06-28 | 浙江省农业科学院 | Method for preparing beta-chitin by utilizing squid cartilage |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4199496A (en) * | 1974-09-05 | 1980-04-22 | Johnson Edwin L | Process for the recovery of chemicals from the shells of crustacea |
| US3906112A (en) * | 1974-09-16 | 1975-09-16 | Bioproducts | Extraction of carotenoid pigment from shrimp processing waste |
| NO147365C (en) * | 1980-11-27 | 1983-03-30 | Jan Raa | PROCEDURE FOR THE MANUFACTURE OF ASTAXANTHIN IN A FORM SUITABLE FOR INCLUSION IN FOR FISHING FISH. |
| US4505936A (en) * | 1983-09-14 | 1985-03-19 | Louisiana State University | Process for the utilization of shellfish waste |
-
1985
- 1985-04-12 DK DK166285A patent/DK157452C/en not_active IP Right Cessation
-
1986
- 1986-04-08 ES ES553767A patent/ES8706170A1/en not_active Expired
- 1986-04-08 IS IS3090A patent/IS1458B6/en unknown
- 1986-04-09 WO PCT/DK1986/000034 patent/WO1986006082A1/en unknown
- 1986-04-09 EP EP86902350A patent/EP0217887A1/en not_active Withdrawn
- 1986-04-09 AU AU56946/86A patent/AU5694686A/en not_active Abandoned
- 1986-04-11 PT PT82378A patent/PT82378B/en unknown
- 1986-04-11 IN IN284/CAL/86A patent/IN165452B/en unknown
- 1986-04-11 AR AR86303626A patent/AR242592A1/en active
- 1986-12-11 NO NO865015A patent/NO165966C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IN165452B (en) | 1989-10-21 |
| DK157452C (en) | 1990-05-21 |
| PT82378A (en) | 1986-05-01 |
| IS3090A7 (en) | 1986-10-13 |
| DK166285A (en) | 1986-10-13 |
| NO865015L (en) | 1986-12-11 |
| DK166285D0 (en) | 1985-04-12 |
| NO165966C (en) | 1991-05-08 |
| AU5694686A (en) | 1986-11-05 |
| IS1458B6 (en) | 1991-01-16 |
| EP0217887A1 (en) | 1987-04-15 |
| WO1986006082A1 (en) | 1986-10-23 |
| ES553767A0 (en) | 1987-06-16 |
| NO165966B (en) | 1991-01-28 |
| AR242592A1 (en) | 1993-04-30 |
| ES8706170A1 (en) | 1987-06-16 |
| PT82378B (en) | 1987-09-08 |
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