CN106749764B - A kind of method for one-step preparation of chitin in shrimp and crab shells by quaternary ammonium salt ionic liquid - Google Patents

Abstract

The invention discloses a kind of methods that quaternary ammonium salt ionic liquid prepares chitin in shrimp and crab shells, belong to chemistry, chemical industry, biological field.This method obtains shrimp and crab shells powder using the extensive shrimp and crab shells in source as raw material, by washing, crushing, drying and other steps.The powder is mixed with quaternary ammonium salt ionic liquid, heating stirring, by quaternary ammonium salt ionic liquid by shrimp and crab shells calcium carbonate and the impurity dissolution removal such as protein, then by shrimp and crab shells insoluble in quaternary ammonium salt ionic liquid chitin washing, be freeze-dried and obtain chitin finished product.It is simple that the present invention relates to process flows, and a kind of quaternary ammonium salt ionic liquid has been only used from raw material to finished product, and without acid, alkali or other medicaments, step dissolution reaction can obtain the chitin finished product of purity >=85%.The chitins derived product such as chitosan, oligosaccharides and Glucosamine can be prepared as raw material.

Description

A kind of method that one step of quaternary ammonium salt ionic liquid prepares chitin in shrimp and crab shells

Technical field

The present invention relates to a kind of method that ionic liquid prepares chitin from shrimp and crab shells, especially a kind of quaternary ammonium salt ionThe method that liquid prepares chitin belongs to chemistry, chemical industry, biological field.

Background technique

Chitin is the second major class polysaccharide material that cellulose is only second in nature, by N- acetylaminohydroxyphenylarsonic acid D-GlucoseRing passes through straight chain polymer made of β-(Isosorbide-5-Nitrae) glucosides key connection, has biomass extremely abundant on earth, mainly depositsIt is in the shell of the crustaceans such as shrimp crab, while is also presently found unique positively charged alkaline polysaccharide substance, it is rightNegatively charged all kinds of harmful substances have excellent suction-operated, have widely in fields such as food, chemical industry, biological medicinesApplication prospect.

The preparation method of industrial chitin is the inorganic salts and protein removed in shrimp and crab shells under the conditions of strong acid concentrated baseObtain chitin.Although this method technology maturation, production procedure is long, at high cost, and the use of a large amount of soda acids will also be damagedEvil environment.And some improved technologies developed in recent years, such as complex enzyme and organic acid processing, fermentation method, microorganism extraction method, byIn at high cost, low efficiency, it can not also obtain industrial scale applications and stagnate in laboratory scale.In addition to this, people also attempt byChitin is dissolved in certain specific solvents, then by stripping agent regenerated come.The crust of report is disclosed at presentPlain solvent has: highly basic inorganic salt system (LiCNS, Ca (CNS)₂、CaI₂、CaBr₂、CaCl₂), highly basic low temperature system (NaOH/ urineElement, NaOH/CS₂), strong acid polar solvent system (dichloroacetic acid, trichloroacetic acid, chlorhydrin), lithium chloride/amide system, fluorinationSolvent etc., ion liquid system ([C₂mim]OAc、[C₄mim]OAc、[C₄Mim] Cl, [Amim] Br etc.).But it is dissolvedChitin, which needs to be regenerated using a large amount of water or alcohol, to be come, so that production procedure is tediously long, and increases production cost, but alsoThe problems such as easily causing product degradation, dissolvent residual, ecological environment is generally limited only to laboratory and manufactures experimently on a small scale.At present not yetSee the report for obtaining the method for high-purity chitin from shrimp and crab shells using one step of single solvent.

Summary of the invention

The problem of preparing chitin the present invention overcomes existing ion liquid dissolving shrimp and crab shells regeneration, proposesMethod except calcium carbonate and protein to obtain higher degree chitin.Using single one step of quaternary ammonium salt ionic liquid by shrimpThe non-chitin ingredient dissolution such as calcium carbonate and protein in crab shell obtains chitin finished product.The purity of the chitin of preparation andHigh income, and this method is easy to operate, process is short, high-efficient, easy to industrialized production.

The method provided by the present invention for preparing chitin from shrimp and crab shells, it is characterised in that by shrimp and crab shells washing, drying, powderIt is broken to obtain shrimp and crab shells powder.The powder is mixed according to a certain percentage with quaternary ammonium salt ionic liquid, heating stirring reaction obtains seasonAmmonium Salt Ionic Liquid/shrimp and crab shells mixed liquor.Directly add water or alcohol to wash in mixed liquor after reaction, is then dried to obtain firstShell element finished product.

After the shrimp and crab shells crush, filtered with water until the conductivity difference of the filtrate filtered twice is no more than2%, the conductivity of filtrate is measured by conductivity meter.

The partial size of shrimp and crab shells is 40~150 mesh after the crushing.

The structural formula of the quaternary ammonium salt ionic liquid isWherein R can be methyl or ethylOne or more, X can be CH₃SO₃^-Or HSO₄^-。

The shrimp and crab shells powder weight is the 2~8% of quaternary ammonium salt ionic liquid weight.

The heating temperature is 100~130 DEG C.

The reaction time be 4~for 24 hours.

The alcohol can be methanol, ethyl alcohol.

The appearance for the chitin finished product that the method is prepared is white or pale yellow powder or particle, purity >=85%.

The purity of the chitin finished product is calculated according to formula (1):

Chitin purity (%)=(1- content of ashes-protein content-fat content-water content) × 100 (1)

Advantage of the method for the present invention compared with existing chitin technology of preparing is: it is only necessary to use a kind of quaternary ammonium salt ionLiquid can by shrimp and crab shells calcium carbonate and the impurity such as protein remove, be then aided with a small amount of water or alcohol and wash chitinNet re-dry；It does not need to handle shrimp and crab shells repeatedly using medicaments such as bronsted lowry acids and bases bronsted lowries used in current industrial production, be not required to yetChitin is dissolved in specific solvent, then regenerates and in stripping agent appropriate, reduces chitin because of dissolutionAnd bring is lost；Preparation method " step " according to the present invention can obtain chitin finished product, and simple process, process is short, to ringBorder is friendly, with the incomparable distinctive feature of existing other technologies.Chitin prepared by the present invention has good turnThe ability for turning to chitosan can be used as raw material and be used to prepare chitosan, oligosaccharides and Glucosamine.

Specific embodiment

Method of the invention is illustrated below by specific embodiment, but the present invention is not limited thereto.

Following experimental methods as described in the examples are unless otherwise specified conventional method；The material and examinationAgent commercially obtains unless otherwise specified.

Embodiment 1

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 150 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shellPowder freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- front three ethylethanolamine methane sulfonates (Me₃N⁺(CH₂)₂OH CH₃SO₃^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 6%.By glass containerIt is placed in 130 DEG C of oil bath and heats and stir 12h formation ionic liquid/shrimp shell mixed liquor, several times are directly added in mixed liquorThe water washing of volume.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are lightYellow particle, purity 92%.

Embodiment 2

Crab shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Crab shell powder after crushingThe partial size at end is 120 mesh.The crab shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by crab shellPowder freeze-drying.Crab shell powder after taking drying, is added to containing N, N, N- dimethyl ethyl ethanol amine methane sulfonates(Me₂EtN⁺(CH₂)₂OH CH₃SO₃^-) ionic liquid glass container in, the weight ratio of crab shell powder and ionic liquid is 5%.It willGlass container, which is placed in 110 DEG C of oil bath, heats and stirs 7h formation ionic liquid/crab shell mixed liquor, adds directly in mixed liquorEnter the ethanol washing of several times volume.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sampleAppearance is white powder, purity 88%.

Embodiment 3

Crab shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Crab shell powder after crushingThe partial size at end is 40 mesh.The crab shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by crab shell powderEnd freeze-drying.Crab shell powder after taking drying, is added to containing N, N, N- front three ethylethanolamine disulfate (Me₃N⁺(CH₂)₂OHHSO₄^-) ionic liquid glass container in, the weight ratio of crab shell powder and ionic liquid is 2%.Glass container is placed in 110 DEG CIt is heated in oil bath and stirs 5h and form ionic liquid/crab shell mixed liquor, the water washing of several times volume is added directly in mixed liquor.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance is white particle, and purity is91%.

Embodiment 4

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 80 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shell mealEnd freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- dimethyl ethyl ethanol amine methane sulfonates (Me₂EtN⁺(CH₂)₂OH CH₃SO₃^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 8%.By glass containerIt is placed in 120 DEG C of oil bath and heats and stir formation ionic liquid/shrimp shell mixed liquor for 24 hours, several times are directly added in mixed liquorThe water washing of volume.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are lightYellow powder, purity 85%.

Embodiment 5

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 120 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shellPowder freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- methyl diethyl ethylene diamine methane sulfonates(MeEt₂N⁺(CH₂)₂OH CH₃SO₃^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 4%.It willGlass container, which is placed in 100 DEG C of oil bath, heats and stirs 4h formation ionic liquid/shrimp shell mixed liquor, adds directly in mixed liquorEnter the methanol washing of several times volume.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sampleAppearance is white particle, purity 90%.

Embodiment 6

Crab shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Crab shell powder after crushingThe partial size at end is 60 mesh.The crab shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by crab shell powderEnd freeze-drying.Crab shell powder after taking drying, is added to containing N, N, N- dimethyl ethyl ethanol amine disulfate (Me₂EtN⁺(CH₂)₂OH HSO₄^-) ionic liquid glass container in, the weight ratio of crab shell powder and ionic liquid is 4%.Glass container is setIt is heated in 120 DEG C of oil bath and stirs 7h and form ionic liquid/crab shell mixed liquor, several times volume is added directly in mixed liquorWater washing.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are whiteGrain, purity 93%.

Embodiment 7

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 60 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shell mealEnd freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- triethyl group ethanol amine methane sulfonates (Et₃N⁺(CH₂)₂OH CH₃SO₃^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 5%.Glass container is placed inIt is heated in 120 DEG C of oil bath and stirs 12h and form ionic liquid/shrimp shell mixed liquor, several times volume is added directly in mixed liquorEthanol washing.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are whitePowder, purity 90%.

Embodiment 8

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 40 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shell mealEnd freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- triethyl group ethanol amine disulfate (Ee₃N⁺(CH₂)₂OHHSO₄^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 4%.Glass container is placed in 130 DEG CIt is heated in oil bath and stirs 9h and form ionic liquid/shrimp shell mixed liquor, the water washing of several times volume is added directly in mixed liquor.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are yellowish coloured particles, purityIt is 91%.

Embodiment 9

Crab shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Crab shell powder after crushingThe partial size at end is 150 mesh.The crab shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by crab shellPowder freeze-drying.Crab shell powder after taking drying, is added to containing N, N, N- methyl diethyl ethylene diamine methane sulfonates(MeEt₂N⁺(CH₂)₂OH CH₃SO₃^-) ionic liquid glass container in, the weight ratio of crab shell powder and ionic liquid is 3%.It willGlass container, which is placed in 110 DEG C of oil bath, heats and stirs 5h formation ionic liquid/crab shell mixed liquor, adds directly in mixed liquorEnter the methanol washing of several times volume.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sampleAppearance is white powder, purity 91%.

Embodiment 10

Crab shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Crab shell powder after crushingThe partial size at end is 60 mesh.The crab shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by crab shell powderEnd freeze-drying.Crab shell powder after taking drying, is added to containing N, N, N- dimethyl ethyl ethanol amine disulfate (Me₂EtN⁺(CH₂)₂OH HSO₄^-) ionic liquid glass container in, the weight ratio of crab shell powder and ionic liquid is 6%.Glass container is setIt is heated in 120 DEG C of oil bath and stirs 6h and form ionic liquid/crab shell mixed liquor, several times volume is added directly in mixed liquorWater washing.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are white powderEnd, purity 89%.

Embodiment 11

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 100 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shellPowder freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- methyl diethyl ethylene diamine disulfate (MeEe₂N⁺(CH₂)₂OH HSO₄^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 4%.Glass container is setIt is heated in 120 DEG C of oil bath and stirs 10h and form ionic liquid/shrimp shell mixed liquor, several times body is added directly in mixed liquorLong-pending water washing.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are whiteParticle, purity 92%.

Embodiment 12

Shrimp shell is impregnated to remove water-soluble substances therein in tap water, then dries, crushes.Shrimp shell meal after crushingThe partial size at end is 120 mesh.The shrimp shell powder is filtered with tap water, until the conductivity of filtrate reaches balance, then by shrimp shellPowder freeze-drying.Shrimp shell meal after taking drying, is added to containing N, N, N- front three ethylethanolamine disulfate (Me₃N⁺(CH₂)₂OH HSO₄^-) ionic liquid glass container in, the weight ratio of shrimp shell meal and ionic liquid is 7%.Glass container is placed in 130DEG C oil bath in heat and stir 10h formed ionic liquid/shrimp shell mixed liquor, directly in mixed liquor be added several times volume secondAlcohol washing.The freeze-dried chitin finished product for obtaining high-purity of chitin powder after washing, sample appearance are yellowish tonerEnd, purity 90%.

Claims (2)

1. a kind of method that quaternary ammonium salt ionic liquid prepares chitin in shrimp and crab shells, it is characterised in that by shrimp and crab shells powder and quaternary ammoniumIonic liquidOne of which mixing, is heated, and stirring, reaction terminatesAfterwards plus water or alcohol washing, be then dried to obtain chitin finished product；The partial size of the shrimp and crab shells powder is 40~150 mesh；It is describedShrimp and crab shells powder and quaternary ammonium salt ionic liquid weight ratio be 2~8%；The heating temperature is 100~130 DEG C；It is describedHeating time be 12~for 24 hours；The alcohol is one of methanol or ethyl alcohol.

2. the chitin finished product of the preparation of method described in claim 1, appearance is white or pale yellow powder or graininess,Purity >=90%.