CN110156916A - A method of extracting shrimp shell chitin - Google Patents
A method of extracting shrimp shell chitin Download PDFInfo
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- CN110156916A CN110156916A CN201910595119.0A CN201910595119A CN110156916A CN 110156916 A CN110156916 A CN 110156916A CN 201910595119 A CN201910595119 A CN 201910595119A CN 110156916 A CN110156916 A CN 110156916A
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- 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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Abstract
A method of shrimp shell chitin is extracted, shrimp shell chitin extractive technique field is related to.Shrimp shell is dissolved first with benzene sulfonic derivative, then carries out solvent thermal reaction, obtains chitin by centrifugation, washing, drying after reaction.P-methyl benzenesulfonic acid and p-hydroxybenzenyl sulfonate of the present invention do not dissolve pure chitin, but can effectively dissolve the other components in shrimp shell, and the purity of chitin can be improved.The chitin sample of purity 90.28% can be obtained using p-methyl benzenesulfonic acid processing shrimp med, it is slightly lower that p-hydroxybenzenyl sulfonate purifies ability, but also can achieve 80% or more.Size is smaller, and the dissolvable ratio of shrimp med solid is bigger, and the chitin purity accordingly obtained is higher.P-methyl benzenesulfonic acid and p-hydroxybenzenyl sulfonate may be implemented to extract shrimp shell chitin, and compared to traditional soda acid alternation response, this extraction process method has the advantages that easy to operate, reservation chitin surface N- acetyl group.
Description
Technical field
The present invention relates to shrimp shell chitin extractive technique fields, are specifically related to a kind of method for extracting shrimp shell chitin.
Background technique
Chitin (Chitin) i.e. β-(Isosorbide-5-Nitrae) -2- acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucose also known as chitin, chitin,
Chitin etc., molecular formula (C8H13O5N)n, it is widely present in insect, Crustaceans and fungi, is that reserves are only secondary in nature
In the second largest natural polysaccharide of cellulose.The basic component units of chitin are N- acetyl-D-glucose amine, they pass through β-
It is closely similar to connect into cellulose with glucose for Isosorbide-5-Nitrae-glucosides key connection, therefore crust is usually considered C2Hydroxyl is by N- acetyl
The cellulose derivative that base replaces.Chitin also has intermolecular hydrogen bonding network as like fibrous element, thus highly crystalline
Change, have the characteristic of not soluble in water, general soda acid and organic solvent, chemical property is highly stable, it is difficult to directly utilize.Chitin
Be mainly used for production chitosan-chitin part deacetylation product.Chitosan can be dissolved in dilute acid soln, be had
Good biodegradability, biocompatibility, antibiotic property and biological adsorption performance, in medicine, weaving, food, papermaking, print
Dye, chemical industry, biological environmental production industry have a wide range of applications, and are usually used in preparing medical dressing, packaging material for food, papermaking addition
Agent, slow releasing carrier of medication etc..
At home and abroad in the market, chitin is almost that production is extracted from shrimp and crab shells entirely.This experiment is produced using Zhanjiang
Starting material of the Penaeus Vannmei shrimp shell as chitin extraction.China's Penaeus Vannmei resource is very rich, main at present
With produce peeled shrimp for export based on, have every year generate few hundred thousand tonnes of shrimp shell leftover bits and pieces, be rich in chitin, protein, minerals, shrimp
The ingredients such as green element.Raw material of these shrimp shells in addition to being used to process feed, fertilizer or chitin extraction, astaxanthin, amino acid on a small quantity,
Major part is taken as waste landfill or abandons, and causes the serious wasting of resources and environmental pollution.Research and development extract crust from shrimp shell
The high-value products such as element can greatly improve the added value of prawn culturing industry.
Traditional separation shrimp shell component to chitin extraction technique as shown in Figure 1, this method using soda acid alternately at
Imurity-removal is managed, wherein hydrochloric acid is especially calcareous ingredient for removing inorganic salts, dissolves out protein, some factories using sodium hydroxide
Family can also be decolourized before end product using hydrogen peroxide.The method principle is very simple, but soda acid all can be to crust
The strand of element generates degradation, and whole process consumes a large amount of inorganic acid and highly basic, and medicament circulating and recovering is difficult, processing
These acid-base waste fluids need additional equipment and workshop investment, inevitably bring certain problem of environmental pollution, these are not
Sharp factor results in chitin product price and remains high and up-trend year by year is presented.
In recent years, also there is the report of research enzymatic isolation method chitin extraction, mainly by proteolytic enzyme protolysate matter, then
Using the ash content and lipid in acid and microwave combination removing shrimp shell, shrimp head, to achieve the purpose that chitin extraction, but this side
Method enzyme cost is excessively high, complicated for operation.Microbial method utilizes the protease generated during bacterium (such as lactic acid bacteria) or fungi fermentation
Carry out chitin extraction with organic acid, the method reaction condition is relatively mild, can be but anti-with recovery section protein and astaxanthin etc.
Between seasonable very long (3-7 days), complex process needs the equipment such as fermentor, and product purity is not high, still needs to inorganic acid alkali processing
Highly finished product can just be obtained.
Benzene sulfonic derivative --- p-methyl benzenesulfonic acid and p-hydroxybenzenyl sulfonate are a kind of non-oxidizing inorganic strong acid, the former
With dissolved lignin, the protein even comprehensive function of cellulose, the latter has been shown to have dissolution kelp, ascidian slag, squid
The ability of the marine products waste such as barbel.Both acid and Ca2+There is very strong binding force, stable crystallization can be formed, wherein to methyl
Benzene sulfonic acid calcium is a kind of important industrial catalyst, can catalyze and synthesize cinnamic acid N-butyl；P-hydroxybenzenyl sulfonate calcium is then treatment
The specific medicament of microvascular disease.
But whether both benzene sulfonic derivatives, which can dissolve chitin, is still unknown, and it is derivative that this experiment is intended to study benzene sulfonic acid
Object handles the feasibility of shrimp shell chitin extraction, is separated off the impurity such as protein, inanimate matter using these one steps of acid, obtains height
The chitin of purity will greatly simplify production technology, provide reference for efficient utilize of shrimp shell resource.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of extraction shrimp shell chitin easy to operate, this method
Chitin surface N- acetyl group can be retained, obtained chitin purity is higher.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a method of extracting shrimp shell chitin, it is first
Shrimp shell is dissolved first with benzene sulfonic derivative, then carries out solvent thermal reaction, is obtained after reaction by centrifugation, washing, drying
Obtain chitin.
Specific step is as follows:
1., shrimp shell pretreatment
Shrimp shell is air-dried, room temperature preservation is sealed；Then shrimp shell is crushed powdering with pulverizer, be then sieved, is placed in dry
It is saved in dry device；
2., the preparation of benzene sulfonic derivative solution
It weighs benzene sulfonic derivative to be dissolved in distilled water, is configured to benzene sulfonic derivative solution；
3., extract shrimp shell chitin
It weighs a certain amount of shrimp shell to be placed in centrifuge tube, a certain amount of benzene sulfonic derivative solution is added in centrifuge tube, makes shrimp
Shell is dissolved in benzene sulfonic derivative solution；It is put into air dry oven and is reacted after sealing, be centrifuged, washed after reaction
It washs, dry acquisition chitin.
The optimal technical scheme of method as extraction shrimp shell chitin of the invention, in preparation method:
The benzene sulfonic derivative solution is p-hydroxybenzenyl sulfonate or p-methyl benzenesulfonic acid.
1. middle shrimp shell is selected from the South America prawn shrimp shell comprising shrimp head and dried small shrimp to step.
Step 1. in by shrimp shell air-dry to moisture be 6.51 ± 0.13%.
Step 1. in sieving retain 80-200 mesh sample and be placed in drier and save.
Step 3. in every 0.04g shrimp shell the benzene sulfonic derivative that 2. concentration that 1mL step is prepared is 0.1-2mol/L is added
Solution.
Step 3. in be put into air dry oven and react 1-3h at 70-90 DEG C after sealing.
Step 3. in take out reaction product after in centrifuge to be centrifuged 2min under the revolving speed of 2600rpm, discard supernatant liquid,
Retain solid matter；Solid matter deionized water is washed twice, dehydrated alcohol is washed one time, is placed in 105 DEG C of baking oven
Drying to constant weight.
Compared with prior art, the invention has the following advantages that
1), p-methyl benzenesulfonic acid and p-hydroxybenzenyl sulfonate do not dissolve pure chitin, but can effectively dissolve in shrimp shell
The purity of chitin can be improved in other components.
2), using 0.40mol/L p-methyl benzenesulfonic acid, 40 mesh shrimp med 2h are handled at 80 DEG C, can obtain purity 90.28%
Chitin sample, it is slightly lower that p-hydroxybenzenyl sulfonate purifies ability, but also can achieve 80% or more.Size is smaller, shrimp med solid
Dissolvable ratio it is bigger, the chitin purity accordingly obtained is higher.
3), after p-methyl benzenesulfonic acid processing, the size of shrimp med bulky grain drops to 500 μm hereinafter, ash content is aobvious from 1mm or so
Writing reduces, and calcium constituent is completely removed, and surface becomes smooth.P-hydroxybenzenyl sulfonate can also dissolve the calcareous of shrimp med surface, completely
Remove CaCO3Diffraction maximum.
4), p-methyl benzenesulfonic acid and p-hydroxybenzenyl sulfonate may be implemented to extract shrimp shell chitin, compared to traditional acid
Alkali alternation response, this extraction process method have the advantages that easy to operate, reservation chitin surface N- acetyl group.
Detailed description of the invention
It is made with reference to embodiments with method of the attached drawing to a kind of extraction shrimp shell chitin of the invention further detailed
It states.
Fig. 1 is the method flow diagram that traditional shrimp shell produces chitin.
Fig. 2 is the schematic diagram of extraction step of the present invention.
Fig. 3 is dissolution situation schematic diagram of the chitin sterling in two kinds of benzene sulfonic derivatives.
Fig. 4 is the influence schematic diagram that benzene sulfonic derivative concentration dissolves ratio to shrimp med solid.
Fig. 5 is the influence schematic diagram for the reaction time ratio being dissolved to shrimp med solid.
Fig. 6 is the influence schematic diagram of shrimp med size prawn street solubility.
Fig. 7 be chitin sterling, shrimp med and after benzene sulfonic derivative extracts chitin sample scanning electron microscopy
Mirror figure.
Fig. 8 is the chemical composition pie chart that latter two chitin sample is extracted through benzene sulfonic derivative.
Fig. 9 be chitin sterling, shrimp med and after benzene sulfonic derivative extracts chitin sample EDX analysis of spectra.
Figure 10 be chitin sterling, shrimp med and after benzene sulfonic derivative extracts chitin sample XRD analysis spectrogram.
Figure 11 be chitin sterling, shrimp med and after p-methyl benzenesulfonic acid extracts chitin sample FT-IR spectrogram.
Specific embodiment
Shrimp shell chitin is extracted using benzene sulfonic derivative, extraction process is as shown in Fig. 2, specific extraction step is as follows:
1., shrimp shell selection and pretreatment
South America prawn shrimp shell is bought from Zhanjiang, Guangdong Province Aquaculture Corporation, which contains shrimp head and shrimp
Skin air-dries to moisture 6.51 ± 0.13%, seals room temperature preservation.Shrimp shell is crushed powdering with pulverizer, is then sieved, by shrimp
Powder is put into plastic centrifuge tube and seals, and is placed in drier and saves.
It is grouped and is numbered according to sieving shrimp med particle size, as shown in table 1.
1 shrimp med particle size of table number
2., the preparation of benzene sulfonic derivative solution
P-methyl benzenesulfonic acid 4.3055-86.11g (or p-hydroxybenzenyl sulfonate 4.35425-87.085g) is weighed respectively, is dissolved
In 250mL distilled water, volumetric flask constant volume is shaken up, that is, is configured to p-methyl benzenesulfonic acid (or the para hydroxybenzene sulphur of 0.1-2mol/L
Acid) solution.
3., extract shrimp shell chitin
The shrimp shell for weighing 0.04g is placed in 2mL centrifuge tube, pipettes 1mL p-methyl benzenesulfonic acid solution with micropipettor
(or p-hydroxybenzenyl sulfonate solution) is dissolved in shrimp shell in benzene sulfonic derivative solution in centrifuge tube.80 DEG C are put into after sealing
In air dry oven, taken out after reacting 0.5-6h.To be centrifuged 2min under the revolving speed of 2600rpm in centrifuge, liquid is discarded supernatant,
Retain solid matter.Solid matter deionized water is washed twice, dehydrated alcohol is washed one time, is placed in 105 DEG C of baking oven
Drying to constant weight.
As a comparison case, above-mentioned shrimp shell is replaced with into chitin sterling, experimental procedure is identical, so as to investigating chitin
Benzene sulfonic derivative can be dissolved in.
One, analysis determining method
1, chemical composition analysis
1., determination of moisture weighs certain mass and (is denoted as M using 105 DEG C of constant weight methods1) sample, be put into dry weighing
Bottle (mass M2) in, 105 DEG C of 4~6h of drying to constant weight (are denoted as M3), moisture content is calculated by formula 2.2.
2., chitin content analysis
It weighing 1g sample to mix with 10mL hydrochloric acid (1mol/L), handles 1h at room temperature, clear water is filtered after rinsing with filter paper, then
Mixed with 10mL sodium hydroxide (1mol/L), be heated to 80 DEG C of processing 2h, clear water rinses, filtering, repetitive operation twice, clean,
Dry weighing, obtains chitin quality, calculates degree by formula 2.3.
3., protein content analysis
Protein content is determined using Kjeldahl's method.0.5g sample, 3.3g copper sulphate and sulfuric acid are put into digest tube
Potassium (1:10) catalyst, the 10mL concentrated sulfuric acid, cover funnelform lid, are placed in digesting, are now heated to 240 DEG C of heat preservation 1h,
420 DEG C of reaction 2h are being warming up to, the liquid in digest tube becomes light green color, closes digesting, natural cooling.Next it is digesting
For the sodium hydroxide of addition 35% until liquid color becomes sepia, heating distillation generates ammonia in pipe, with containing methyl red/bromine first
2% boric acid solution of the green indicator of phenol absorbs ammonia, then is titrated with standard hydrochloric acid (0.1mol/L).Record the hydrochloric acid volume of consumption
(V1, blank sample V0), protein content is calculated by formula 2.4.
Wherein, 0.1 be standard hydrochloric acid solution concentration, 14 be the molecular mass of N, 6.25 be N be converted into protein be
Number, 0.5 is the quality of sample.
4., fats the extractives content analysis
It is measured with soxhlet extraction methods.10g, 105 DEG C of samples dried are weighed, the pre- filter paper packet extracted is encapsulated in
In, it is placed in Soxhlet extractor, injects 500mL ether, heating extracting, control temperature just makes ether every 1h reflux 7 times or more.
After extracting 4h, fat to the greatest extent is taken out, paper bag is taken out.Continuous heating removes condenser pipe and extracting barrel, to ether close to siphon pipe height
Ether is transferred to weighing bottle out, and remaining ether is dried 2h at 80 DEG C, the net weight of weighing bottle content is weighed, based on formula 2.5
Calculate fat content.
5., inanimate matter content of ashes analysis
It is measured by calcination method, weighs 1g sample (being accurate to 0.0001g) first and be placed on crucible with cover, electric furnace has been ashed
Crucible is placed in calcination 30min in Muffle furnace (550 DEG C), is put into drier and weighs after cooling, calculate by formula 2.6 by Quan Hou
Content of ashes.
2, surface chemist reaction
1., the measurement of FTIR spectrum
Tabletting after sample is diluted with KBr, lamp shine drying, exclude moisture and interfere caused by hydroxyl peak-to-peak signal.In Bruker
Test sample is in 4000~400cm of wave-length coverage on Fourier infrared spectrograph-1Infrared absorption spectrum, resolution ratio is set as 4cm-1,
Scanning speed is 0.2cm-1/ s, number of background scan are 64 times, and number of sample scan is 32 times.
2., X-ray diffraction
All samples are made to 40 μm of diameter of dry particle, prepare parallel sample, every part of 5g, in a Japan
It is tested on RIGAKUD/max-IIIA type X-ray diffractometer, test uses copper target, tube voltage 35kV, tube current 30mA, starting
10 ° of angle, 80 ° of end angle, step width 0.01, wavelength 1.54056, speed is set as 8 °/min.
③、EDX-SEM
Using FEI Co., U.S. Q45 scanning electron microscope and Bruker company XFlash6130 X-ray energy spectrometer into
Row scanning, parameter setting are as follows: voltage 10kv, beam spot 4.0, enlargement ratio 40-1000, distance 11.5, humidity 46%, temperature 23
℃。
Two, shrimp med chitin feasibility study is extracted using benzene sulfonic derivative
1, the ingredient of shrimp med raw material
Shrimp shell is crushed, obtains shrimp med after sieving, as shown in Fig. 2, by detection it can be seen that its main component contains
Protein (28.58%), chitin (27.95%), inorganic ash content (23.94%) and fatty (7.90%), other compositions (such as water
Dissolubility, hot volatility, pyrolytic) at subtotaling accounting 11.63%.It theoretically calculates, every 1kg over dry shrimp med most multipotency produces
Raw 279.5g chitin.According to the result of study of Zhang Xianggang et al., chitin accounts for South America prawn shrimp head and (over dry) of dried small shrimp compares
It is 15.4% and 26.8% respectively again, the relatively low content that they test is because using fresh shrimp shell, and water content is high, all
Multicomponent is all kept down.Used in this application is the shrimp shell air-dried, houses or so half a year, may have many ingredients to exist
It volatilizees or is decomposed by the microorganisms during this.Sun Qian et al., which is measured, carrys out Penaeus Vannmei dry powder containing chitin content
25.16%, it is as a result to be closer to this experiment.
2, solvability of two kinds of benzene sulfonic derivatives to chitin
The application has found that two kinds of benzene sulfonic derivatives cannot dissolve pure chitin.It is pure according to above method measurement chitin
The moisture content of product is shown in Table 2, and moisture is 6.90 ± 0.08%.
2 chitin moisture data of table
In conjunction with above-mentioned comparative example, chitin is dissolved using toluenesulfonic acid, accounts for sample by measuring dry solids quality
The ratio of product (moisture content 6.90 ± 0.08%) is between 93.5%~94.2% (as shown in Figure 3), with untreated control sample
Product are compared except the solid content after moisture 93.10%, are not declined, and are slightly risen instead.P-hydroxybenzenyl sulfonate with to methyl
Benzene sulfonic acid test result is similar, does not cause substantially reducing for solid matter.This shows chitin in p-methyl benzenesulfonic acid and right
It cannot be dissolved in hydroxy benzene sulfonic acid, therefore can be used to purification chitin.In fact, a large amount of studies have shown that natural first
Shell element (not sufficiently removing N- acetyl group) cannot be dissolved in low concentration strong inorganic acid (such as hydrochloric acid), and two kinds of benzene sulfonic derivatives do not have
Oxidizing, main function is the acid soluble substance of dissolution.But it is anti-that with carbohydrate derivatization may occur for both acid
It answers, forms ester bond, cause the rising of solid quality, this possibility has been discussed in subsequent experimental.
3, the solvability of two kinds of benzene sulfonic derivative prawn shells
1., the influence of acid concentration
It is tested using the 40-200 mesh shrimp med of moisture content 6.5% (similarly hereinafter), 0.1 is dispersed in by above-mentioned steps~
In the p-methyl benzenesulfonic acid (or p-hydroxybenzenyl sulfonate) of 2mol/L, measurement dry solids quality accounts for the ratio of sample after the completion of processing
Value deducts moisture 6.5%, dissolution ratio is calculated by formula 2.7, data are plotted in Fig. 4.
As seen in Figure 4, the dissolution of shrimp med solid is more sufficiently complex than with the relationship of acid concentration, in low acid concentration (0.1
~0.4mol/L) when, acid concentration is higher, and stripping material is more, the substantially linear relationship of the two；In 0.4~0.8mol/ of acid concentration
Within the scope of L, dissolution ratio reaches peak value, and p-methyl benzenesulfonic acid is slightly above p-hydroxybenzenyl sulfonate；Acid concentration 0.8~2mol/L range
It is interior, acid it is more, be more easy to happen derivative reaction, remain in it is more on solid, be reflected in Fig. 4 then show dissolution ratio with acid
Concentration increases and declines.
2., the influence in reaction time
Time deficiency is likely to result in being not thorough for shrimp shell component dissolution, this experiment has been investigated under the conditions of 80 DEG C, dissolution 0
Leachable accounts for the ratio of over dry raw material after~6h, as a result as shown in Figure 5, it is clear that, 2h is reacted, shrimp med solid dissolution ratio can approach
Peak value, persistently the increase reaction time cannot improve the dissolving ratio of solid matter (mainly chitin).
3., the influence of shrimp med size
Dissolution experiment is done with various sizes of shrimp med in 0.8mol/L p-methyl benzenesulfonic acid and table 1, after reacting 2h, as a result such as
Shown in Fig. 6 a and 6b, it is clear that size is an important factor for influencing shrimp med dissolution, and all in all, size is smaller, and dissolution ratio is higher.
By taking Fig. 6 a result as an example, the dissolution of different meshes shrimp med is than sequence are as follows: No. 5 (80-200 mesh) > No. 3 (40-200 mesh) > No. 1 (20-
200 mesh) > No. 4 (40-80 mesh) > No. 2 (20-40 mesh), it is clear that the particle containing low mesh number, small size is more, and dissolution ratio is higher.
For mesh number in 80-200 mesh, the treatment effect of p-methyl benzenesulfonic acid prawn shell is best, and dissolution is than being equivalent to up to 68.38%
85.5% purity.P-hydroxybenzenyl sulfonate is to the shrimp med of different meshes dissolution law having the same, and maximum dissolution is than slightly lower
(65.63%), the chitin of purity about 74.1% is obtained.In general, grinding is most readily available small size under drying regime
Shrimp med particle, size is smaller, and bigger with the contact area of solvent, reaction rate is bigger, the dissolution specific efficiency of alkaline soluble materials
It is higher.
Three, shrimp med chitin pattern and chemical composition analysis are extracted using benzene sulfonic derivative
1, SEM and chemical composition analysis
Using the benzene sulfonic derivative of 0.4mol/L at 80 DEG C of 40-200 mesh shrimp med samples handled (reaction 2h), mentioned
Pure chitin sample.First to 4 groups of samples (a-d successively represent chitin sterling, shrimp med, p-methyl benzenesulfonic acid processing sample,
P-hydroxybenzenyl sulfonate handles sample) Analysis of Surface Topography has been done, as a result as shown in Figure 7.Firstly, derivative by p-methyl benzenesulfonic acid
The size of the processing of object, shrimp med bulky grain drops to 500 μm hereinafter, the calcium particle that particle surface covers is shown from 1mm or so
It writes and reduces, surface becomes smooth.But p-hydroxybenzenyl sulfonate is obvious not as p-methyl benzenesulfonic acid to size reduction, and some
Particle surface also retains apparent calcified plaque, which reflects p-hydroxybenzenyl sulfonate processing deliming and is not thorough.Chemical constituent
Protein and ash composition in shrimp med have been confirmed benzene sulfonic derivative really and can have been got rid of in analysis (result is in fig. 8),
High temperature removing impurities improve the purity of chitin, wherein p-methyl benzenesulfonic acid treated sample purity reaches 90% with
On, compared to traditional acid-alkali washing repeatedly, it is greatly simplified purification step.Fig. 8 also demonstrates that SEM in Fig. 7 is observed as a result, aobvious
Right p-methyl benzenesulfonic acid processing removes most inorganic constituents, and it is a little right that a small amount of ingredient is likely to have in washing process
Caused by toluenesulfonic acid calcium is redeposited.And the sample that p-hydroxybenzenyl sulfonate is handled remains a large amount of ash component,
It may be it caused by rear solubility is low in conjunction with Ca.
2, surface-element composition analysis
Surface-element composition analysis is done to aforementioned four sample using energy dispersion X-ray spectrometer (EDX), is as a result distinguished
It is organized into Fig. 9 and table 3.Obviously, the commodity chitin that this experiment uses is not a hundred percent decalcification, surface calcium constituent specific gravity
0.15% (Fig. 9 a) also detects the elements such as sodium, magnesium, aluminium, silicon other than calcium, these elements are composition inorganic ash contents
Common elements.Commodity chitin does not contain P and S element, both elements are element common in nucleic acid and protein respectively.Quotient
Product chitin surface nitrogen content 2.21%, lower than theoretical nitrogen content 8.7%, this may be the soda acid alternating due to production chitin
The processed part N- acetyl group for removing one layer of chitin molecule of most surface, and due to fine and close crystalline texture, acid, base molecule
The substance inside particle can not be attacked.
Ironically, untreated shrimp med surface more than chitin control sample P element (Fig. 9 b), it should come from
The intracorporal cellular material of shrimp, such as sugar, the protein molecule of nucleic acid, phosphorylation.Untreated shrimp med surface nitrogen element content is very
Height, but it is far below the percentage of ash content, this illustrates although calcium constituent concentrates on surface, but is likely to be covered with there are also other substances
Calcified layer.
The chitin that p-methyl benzenesulfonic acid is handled does not detect calcium constituent (Fig. 9 c) completely, and the ratio of surface N element
Example has reached 8.35%, and very close theoretical value, this result effectively supports above-mentioned experimental result, this shows to methyl
Benzene sulfonic acid avoids the destruction of surface N- acetyl group while isolating and purifying chitin, this is surface-functionalized for chitin
Modification is highly advantageous.In addition, sample surfaces have had more S element, this declaratives p-methyl benzenesulfonic acid has occurred with chitin
The hydroxyl of reaction, the sulfonic acid group of element containing S and carbohydrate may have occurred esterification, this will cause sample solid masses
Increase, with it is above-mentioned the result is that completely it is corresponding.
Although the processing of p-hydroxybenzenyl sulfonate also improves the ratio of chitin, not enough thoroughly, still remain about
20% calcareous (Fig. 9 d), this is also to meet with aforementioned result.
The surface-element of several chitin samples of table 3 forms
3, crystal analysis
X-ray crystal diffraction (XRD) analysis is done to above-mentioned four kinds of samples, as a result in Figure 10.Most apparent from former shrimp med
Sample is located at 2 θ=29.4 °, and there are a strong CaCO3Diffraction maximum, by the processing of two kinds of benzene sulfonic derivatives, this spreads out
Peak to be penetrated to disappear, this shows that p-methyl benzenesulfonic acid and p-hydroxybenzenyl sulfonate can effectively be reacted with the calcified layer on shrimp shell surface,
Ca ion isolation is come out, in conjunction with sulfonic acid group, is respectively formed p-methyl benzenesulfonic acid calcium and p-hydroxybenzenyl sulfonate calcium.But the former
Solubility is high, is not easy to deposit in subsequent operation, therefore, morphology analysis, chemical composition analysis and elemental analysis all do not detect
The presence of calcium；And the latter is attached to chitin sample surfaces probably because being easy deposition, although diffraction maximum disappears, they
Exist in the form of amorphous pellets, on the sem picture, then surface is reflected in chemical composition then table by the patch being cracked for reflection
Content now for ash content and calcium constituent is still significant.
4, FT-IR is analyzed
Shrimp med (label shrimp) to chitin (label Chitin), untreated 40-200 mesh and utilize 0.40mol/
The sample that the p-methyl benzenesulfonic acid processing 2h of L is obtained carries out FT-IR Spectral Identification, is as a result summarized in Figure 11.898cm in figure-1
Left and right belongs to the absorption peak of ring stretching vibration, 1020~1160cm-1Left and right is the absorption peak of C-O stretching vibration, 1350cm-1It is left
The right side is III bands of a spectrum of amide, it is clear that in this position, chitin and p-methyl benzenesulfonic acid handle sample and had more one significantly than former shrimp med
Absorption peak, in addition, they are than former shrimp med in 1555cm-1The left and right peak amide II and 1650cm-1The opposite letter of left and right amide I peaks
It number is remarkably reinforced, peak is more sharp, this is to have corresponded to chitin in the promotion of surface concentrations.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (9)
1. it is a kind of extract shrimp shell chitin method, which is characterized in that first with benzene sulfonic derivative dissolve shrimp shell, then into
Row solvent thermal reaction, after reaction by centrifugation, washing, dry acquisition chitin.
2. extracting method as described in claim 1, which is characterized in that specific step is as follows:
1., shrimp shell pretreatment
Shrimp shell is air-dried, room temperature preservation is sealed；Then shrimp shell is crushed powdering with pulverizer, is then sieved, is placed in drier
Middle preservation；
2., the preparation of benzene sulfonic derivative solution
It weighs benzene sulfonic derivative to be dissolved in distilled water, is configured to benzene sulfonic derivative solution；
3., extract shrimp shell chitin
It weighs a certain amount of shrimp shell to be placed in centrifuge tube, a certain amount of benzene sulfonic derivative solution is added in centrifuge tube, keeps shrimp shell molten
In benzene sulfonic derivative solution；It is put into air dry oven and is reacted after sealing, after reaction through centrifugation, washing, dry
Dry acquisition chitin.
3. extracting method as claimed in claim 2, which is characterized in that the benzene sulfonic derivative solution is p-hydroxybenzenyl sulfonate
Or p-methyl benzenesulfonic acid.
4. extracting method as claimed in claim 2 or claim 3, which is characterized in that step 1. in shrimp shell be selected from include shrimp head and dried small shrimp
South America prawn shrimp shell.
5. extracting method as claimed in claim 2 or claim 3, which is characterized in that step 1. in by shrimp shell air-dry to moisture be 6.51
± 0.13%.
6. extracting method as claimed in claim 2 or claim 3, which is characterized in that step 1. set by middle sieving reservation 80-200 mesh sample
It is saved in drier.
7. extracting method as claimed in claim 2 or claim 3, which is characterized in that step 3. in every 0.04g shrimp shell 1mL step is added
2. the concentration prepared is the benzene sulfonic derivative solution of 0.1-2mol/L.
8. extracting method as claimed in claim 2 or claim 3, which is characterized in that step 3. in sealing after be put into air dry oven
1-3h is reacted at 70-90 DEG C.
9. extracting method as claimed in claim 2 or claim 3, which is characterized in that step 3. in take out reaction product after in centrifuge
In to be centrifuged 2min under the revolving speed of 2600rpm, discard supernatant liquid, retain solid matter；Solid matter is washed with deionized water
Twice, dehydrated alcohol is washed one time, is placed in 105 DEG C of baking oven that drying to constant weight.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880981A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for synthesizing phosphorylated chitin by taking methanesulfonic acid as solvent |
| US20160060363A1 (en) * | 2014-08-27 | 2016-03-03 | The Board Of Trustees Of The University Of Alabama | Chemical pulping of chitinous biomass for chitin |
| CN108912244A (en) * | 2018-06-15 | 2018-11-30 | 浙江万里学院 | From crab shell one step decalcification, de- albumen, degreasing fat chitin extraction method |
| CN109517090A (en) * | 2017-09-18 | 2019-03-26 | 中国科学院金属研究所 | A kind of preparation method of the degree of polymerization and the controllable labyrinth chitosan oligosaccharide of deacetylation |
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2019
- 2019-07-03 CN CN201910595119.0A patent/CN110156916A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880981A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for synthesizing phosphorylated chitin by taking methanesulfonic acid as solvent |
| US20160060363A1 (en) * | 2014-08-27 | 2016-03-03 | The Board Of Trustees Of The University Of Alabama | Chemical pulping of chitinous biomass for chitin |
| CN109517090A (en) * | 2017-09-18 | 2019-03-26 | 中国科学院金属研究所 | A kind of preparation method of the degree of polymerization and the controllable labyrinth chitosan oligosaccharide of deacetylation |
| CN108912244A (en) * | 2018-06-15 | 2018-11-30 | 浙江万里学院 | From crab shell one step decalcification, de- albumen, degreasing fat chitin extraction method |
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Application publication date: 20190823 |