CN107312109A - Chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid - Google Patents
Chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid Download PDFInfo
- Publication number
- CN107312109A CN107312109A CN201610265885.7A CN201610265885A CN107312109A CN 107312109 A CN107312109 A CN 107312109A CN 201610265885 A CN201610265885 A CN 201610265885A CN 107312109 A CN107312109 A CN 107312109A
- Authority
- CN
- China
- Prior art keywords
- shrimp
- deliming
- crab shells
- ionic liquid
- citric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Genetics & Genomics (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Analytical Chemistry (AREA)
- Biophysics (AREA)
- Sustainable Development (AREA)
- Meat, Egg Or Seafood Products (AREA)
Abstract
The invention provides chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid, this method comprises the following steps：(1) remove the calcium in shrimp and crab shells using the step deliming method of citric acid two and obtain deliming shrimp and crab shells；(2) protein in degradable ion liquid dissolving deliming shrimp and crab shells, isolated chitin are utilized.The present invention is by using the step deliming method of citric acid two, it is combined with the protein in degradable ion liquid dissolving deliming shrimp and crab shells, so that the chitin in shrimp and crab shells is separated, at the same time the calcium citrate obtained is food Creta Preparata, the high value added product in addition to chitin can be produced, and also isolated protein, realize the full constituent of discarded shrimp and crab shells, higher value application, turn waste into wealth, generation environment does not pollute, solve existing shrimp and crab shells and prepare the environmental problem caused in chitin technology using hydrochloric acid deliming and alkali removing protein, with extensive prospects for commercial application.
Description
Technical field
The invention belongs to waste resource recycling field, it is related to a kind of separating and extracting process of chitin, especially
It is to be related to chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid.
Background technology
With China marine product industry and propagate shrimp, crab industry artificially and develop rapidly, in process it is annual about
1,000 ten thousand tons of discarded shrimp, crab shell can be produced.Due to the shortage of process and utilization technology, these shrimps, crab shell are given up
Gurry is largely served only for the low value-added products such as production feed, fertilizer, or even is stacked, arbitrarily due to direct
Abandon, cause offshore, coastal air it is rancid, severe contamination environment.But containing rich in shrimp, crab shell
Rich calcium (content about 30-40%) protein (content constitutes about 20-30%), (content is about for chitin
Account for 15-30%) etc. valuable high-quality living resources, if these materials are separated and high efficiente callback is utilized,
High-valued product is prepared, shrimp, crab shell economic value can be achieved and significantly rises in value.
The method of industrial chitin extraction most of at present is mainly strong acid concentrated base high temperature method, and the first step is used
Calcium in dissolving with hydrochloric acid shrimp, crab shell, not only with severe corrosive, and produces a large amount of waste liquids, there is environment
Pollution.Second step dissolves the protein in deliming shrimp, crab shell using highly basic, and highly basic can produce substantial amounts of height
Concentration waste liquid, severe contamination environment.Other protein and chitin are not with the shape that dissociates in shrimp, crab shell
What state was present, but symbiosis is combined together by polyhydroxy phenol crosslinking and forms glycoprotein, generate proteoglycans
Compound.The symbiotic structure of protein and chitin is to cause protein separated and dissolved from shrimp, crab shell not thorough
One difficulties at bottom.And the conventional processing method of protein is except using highly basic in current shrimp, crab shell
Dissolved, another is digested with protease, but protease price is more expensive, and percent hydrolysis is low,
Need to repeatedly it digest, and condition is harsh.
CN103757079A discloses a kind of Separation extraction method of chitin, and methods described is with crust
Class animal waste is that Raw material processing produces protein hydrolysate and chitin, and it first dries shrimp shell or crab shell, then
It is crushed in 40-80 mesh input digestion tank and adds water and stir, stands be swelled at normal temperatures；Then, by digestion
Tank is heated to 51-55 DEG C, adds mixed enzyme by the percentage by weight of input shrimp shell powder raw material 0.6%, adjusts pH value
For 6.5-7.5, press filtration obtains digestion refined filtration liquid and net shrimp shell meal after stirring digestion；Refined filtration liquid is centrifuged, under
Layer remaining liq is after decolouring, secondary fine filtering, desalination, then through being concentrated in vacuo, being spray-dried and obtaining protein hydrolysate
Powder product；Hydrochloric acid solution is added to soak after decalcification back end hydrogenation sodium oxide molybdena to neutrality through filtering, cleaning, baking in net shell powder
Do to obtain chitin.The method of the invention is related to pretreatment of raw material, mixed enzyme digestion, column chromatography desalination, hydrolysis
Albumen powder is prepared and chitin preparation process, more complicated, and because the use of hydrochloric acid can increase chlorion
Pollution to water, and hydrochloric acid, the corrosivity of sodium hydroxide etc. are strong, and usage amount is improper to cause environmental pollution.
Therefore, in this area, it is necessary to develop a kind of chitin extraction separation method of more economical and efficient environmental protection.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of separating and extracting process of chitin,
It is provided in particular in chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid.For up to this
Purpose, the present invention uses following technical scheme：
On the one hand, the present invention provides a kind of separating and extracting process of chitin, the described method comprises the following steps：
(1) remove the calcium in shrimp and crab shells using the step deliming method of citric acid two and obtain deliming shrimp and crab shells；
(2) protein in degradable ion liquid dissolving deliming shrimp and crab shells, isolated chitin are utilized.
In the present invention, the recycling of calcium in shrimp and crab shells raw material can be realized by using methods described, with
And full component, the higher value application of shrimp and crab shells discarded object can be realized with isolated protein and chitin.
Preferably, step (1) the step deliming method of citric acid two comprises the following steps：
A, using citric acid solution dissolve shrimp and crab shells, be filtrated to get a deliming shrimp and crab shells and a citric acid
Filtrate；
B, using citric acid solution dissolve a deliming shrimp and crab shells, be filtrated to get secondary deliming shrimp and crab shells and secondary
Citric acid filtrate；
C, respectively the addition calcium citrate crystal seed into a citric acid filtrate and secondary citric acid filtrate, stand analysis
Go out calcium citrate.
Preferably, the mass percent concentration of citric acid solution described in step A be 8-15%, such as 8%,
9%th, 10%, 11%, 12%, 13%, 14% or 15%.
Preferably, citric acid solution described in step A and shrimp shell mass ratio are 5-8:1, such as 5:1、5.2:1、
5.4:1、5.6:1、5.7:1、5.8:1、5.9:1、6:1、6.2:1、6.4:1、6.6:1、6.8:1、7:1、7.3:1、
7.5:1、7.8:1 or 8:1.
Preferably, the time of citric acid solution dissolving shrimp and crab shells is 2-4 hours described in step A, and such as 2 is small
When, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6
Hour, 3.8 hours or 4 hours.
Preferably, described in step A dissolve when temperature be 10-30 DEG C, such as 10 DEG C, 12 DEG C, 14 DEG C,
16 DEG C, 18 DEG C, 20 DEG C, 22 DEG C, 24 DEG C, 26 DEG C, 28 DEG C or 30 DEG C.
Preferably, the mass percent concentration of citric acid solution described in step B be 4-10%, such as 4%,
4.5%th, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10%
Preferably, citric acid solution described in step B and a deliming shrimp and crab shells mass ratio are 4-6:1, for example
4:1、4.2:1、4.4:1、4.6:1、4.7:1、4.8:1、4.9:1、5:1、5.2:1、5.4:1、5.6:1、5.8:1
Or 6:1.
Preferably, described in step B dissolve a deliming shrimp and crab shells time be 1-3 hours, such as 1 hour,
1.3 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours
Or 3 hours.
Preferably, described in step B dissolve when temperature be 10-30 DEG C, such as 10 DEG C, 12 DEG C, 14 DEG C,
16 DEG C, 18 DEG C, 20 DEG C, 22 DEG C, 24 DEG C, 26 DEG C, 28 DEG C or 30 DEG C.
Preferably, the addition of calcium citrate crystal seed described in step C is the 1-5% of the theoretical amount of precipitation of calcium citrate,
Such as 1%, 1.3%, 1.5%, 1.8%, 2%, 2.4%, 2.8%, 3%, 3.4%, 3.8%, 4%, 4.4%,
4.8% or 5%.
Preferably, step A and step B is supplemented into the citric acid solution after precipitation calcium citrate described in step C
The 25-35% (such as 25%, 27%, 29%, 30%, 32%, 34% or 35%) of the citric acid total amount used
After can be recycled.
In the present invention, the method for calcium removed in shrimp and crab shells needs to use two-step method as described above, be because
Citric acid solution dissolving shrimp and crab shells are added to be disposable, if acid concentration is slightly higher, though deliming rate is high (being more than 98%)
But the calcium citrate of generation has been dissolved into citric acid again, no longer separate out or amount of precipitation is few.If acid concentration
Low, though the calcium citrate amount of precipitation is more, to remove calcium in shrimp and crab shells, not exclusively, deliming rate is low.
In two-step method deliming technique, the addition total amount of citric acid is roughly the same with the disposable citric acid total amount that adds twice,
And using step deliming method (i.e. first time citric acid concentration and acid total amount relative to higher for the second time, first
Secondary deliming make it that after the most of calcium dissolving of shrimp and crab shells that then shrimp and crab shells connection loosing reuses concentration relatively low
Second hypo acid deliming), so deliming rate is higher (being more than 98%)；But be divided into disposable citric acid amount
Two parts are carried out deliming respectively, are then filtered, a citric acid filtrate and citric acid filtrate separates out lemon respectively twice
Sour calcium, because filtrate acid amount twice is all little respectively, so the calcium citrate separated out respectively will not dissolve again
Enter in primary and secondary citric acid filtrate, so two-step method deliming technique, can both ensure shrimp and crab shells deliming rate,
Calcium citrate amount of precipitation can be ensured again.
Preferably, step (2) the degradable ionic liquid is choline amino acid ion liquid.
Preferably, step (2) the degradable ionic liquid is choline glycine ionic liquid, the ammonia of choline third
Acid ion liquid, choline leucine ionic liquid, choline serine ionic liquid, choline lysine ionic liquid
Body, choline ionotropic glutamate liquid, choline aspartic acid ionic liquid, choline phenylalanine ionic liquid,
Choline tryptophan ionic liquid, choline isoleucine ionic liquid, choline threonine ionic liquid, choline figured silk fabrics
Propylhomoserin ionic liquid, choline arginine ionic liquid, choline histidine ionic liquid, choline paddy amic acid from
Sub- liquid, choline proline ionic liquid, choline methionine ionic liquid or choline N acid ion
In liquid any one or at least two combination.
In the present invention, the title and ionic structure of the choline amino acid ion liquid are as shown in the table：
Preferably, the mass ratio of step (2) the degradable ionic liquid and deliming shrimp and crab shells is 5-20:1,
Such as 5:1、5.3:1、5.5:1、5.8:1、6:1、6.5:1、6.8:1、7:1、8:1、9:1、10:1、11:1、
12:1、13:1、14:1、15:1、16:1、17:1、18:1、19:1 or 20:1.
Preferably, step (2) protein using in degradable ion liquid dissolving deliming shrimp and crab shells
Temperature be 80-130 DEG C, such as 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C,
120 DEG C, 125 DEG C or 130 DEG C.
Preferably, step (2) protein using in degradable ion liquid dissolving deliming shrimp and crab shells
Time be 4-6 hours, such as 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours,
5.3 hours, 5.5 hours, 5.8 hours or 6 hours.
Preferably, described be separated into of step (2) is separated by filtration, because degradable ionic liquid can dissolve deliming
Protein in shrimp and crab shells, but chitin is not almost dissolved, therefore be isolated by filtration, first can be obtained
Shell element product.
Preferably, the protein utilization regenerated solvent of dissolving regenerates protein in step (2).
Preferably, the regenerated solvent is water and/or ethanol.
Preferably, regenerate after the degradable ionic liquid after protein separates with regenerated solvent, to degradable
Can be circulated after the 10-20% that step (2) described degradable ionic liquid usage amount is supplemented in ionic liquid makes
With, be recycled for multiple times effect with it is first quite.
In the removal shrimp and crab shells described in step of the present invention (2) in protein processes, degradable ionic liquid is utilized
Body, is because it has very strong solvability to protein, although many non-degradability ionic liquids pair
Protein also has good dissolubility, but is due to its non-biodegradable, in addition some non-degradabilities from
Sub- liquid has toxicity, these ionic liquids as solvent once in industrialization large-scale use, during
It is possible some can be lost in environment, or remain to organism produce harm.And degradable ionic liquid
The features such as body environmental protection, easily biological-degradable, provided as green solvent for industrial environmental problem
It is good to ensure.
As optimal technical scheme, the separating and extracting process of chitin of the present invention specifically includes following steps：
(1) using mass percent concentration for 8-15% citric acid solution in dissolving shrimp and crab shells at 10-30 DEG C
2-4 hours, the citric acid solution was 5-8 with shrimp shell mass ratio:1, be filtrated to get deliming shrimp and crab shells and
Citric acid filtrate；Using the citric acid solution that mass percent concentration is 4-10% in dissolving at 10-30 DEG C
Deliming shrimp and crab shells 1-3 hours, the citric acid solution and a deliming shrimp and crab shells mass ratio are 4-6:1,
It is filtrated to get secondary deliming shrimp and crab shells and secondary citric acid filtrate；Respectively to a citric acid filtrate and secondary lemon
The 1-5% of the theoretical amount of precipitation of calcium citrate calcium citrate crystal seed is incorporated as in lemon acidleach liquid, stands and separates out lemon
Sour calcium, obtains deliming shrimp and crab shells；
(2) it is small in dissolving the protein 4-6 in deliming shrimp and crab shells at 80-130 DEG C using degradable ionic liquid
When, the mass ratio of the degradable ionic liquid and deliming shrimp and crab shells is 5-20:1, it is separated by filtration and obtains crust
Element.
Described in the present invention " shrimp and crab shells " refer to shrimp shell and/or crab shell.
Relative to prior art, the invention has the advantages that：
The present invention is combined with degradable ion liquid dissolving deliming shrimp by using the step deliming method of citric acid two
Protein in crab shell so that the chitin in shrimp and crab shells is separated, the calcium citrate at the same time obtained
It is food Creta Preparata, can produces the high value added product in addition to chitin, and also isolated egg
White matter, realizes full component, the higher value application of discarded shrimp and crab shells, turns waste into wealth, and sublimity pollution is not produced,
Solve existing shrimp and crab shells and prepare the environment caused in chitin technology using hydrochloric acid deliming and alkali removing protein and ask
Topic, with extensive prospects for commercial application.
Embodiment
Technical scheme is further illustrated below by embodiment.Those skilled in the art
It will be clearly understood that the embodiment is only to aid in understanding the present invention, the concrete restriction to the present invention is not construed as.
Embodiment 1
In the present embodiment, separation and Extraction chitin by the following method, specifically includes following steps：
(1) the new fresh shrimp shell that 0.500g is dried is put into 100mL beakers, adds 3.0g 10% lemon
Lemon acid, reacts 2 hours, filters to obtain a deliming shrimp shell and a citric acid filtrate, 1.5g is then added again
6% citric acid, react 1 hour, secondary deliming shrimp shell and secondary citric acid filtrate are filtered to obtain, by a lemon
Lemon acidleach liquid and secondary citric acid filtrate are placed respectively, are separately added into 0.005g calcium citrate crystal seeds, 10 hours
After separate out calcium citrate, 0.1622g altogether, deliming rate is more than 99%；It will filter out the filter after calcium citrate
Liquid merges, and supplements 1.200g 10% citric acid solution, can recycle.
(2) deliming shrimp shell is dissolved using choline alanine ([Cho] [Ala]) ionic liquid 5g, at 110 DEG C
Stirring 4 hours.Reaction terminates, and chitin 0.1800g is obtained after the filter residue and drying of filtering.Ion after filtering
Liquid regenerates protein 0.1200g using ethanol, is spin-dried for after ethanol, supplements ionic liquid 1g, can continue
Recycle.
Embodiment 2
Difference from Example 1 is, secondary deliming shrimp shell and secondary citric acid are filtered to obtain in step (1)
Filtrate, a citric acid filtrate and secondary citric acid filtrate are placed respectively, 0.0025g lemons are separately added into
Sour calcium crystal seed, separates out calcium citrate, altogether 0.1422g after 10 hours, deliming rate is more than 99%；Except this
Outside method therefor and remaining condition selection it is same as Example 1.
Embodiment 3
Difference from Example 1 is, when dissolving shrimp shell is with secondary deliming shrimp shell is dissolved in step (1),
It is used be 3g 10% citric acid solution will, in addition the selection of method therefor and remaining condition with
Embodiment 1 is identical, separates out 0.1320g calcium citrates, and deliming rate is more than 99%.
Embodiment 4
Difference from Example 1 is, step (2) the ion liquid dissolving deliming shrimp shell reaction temperature
80 DEG C, stir 6 hours, in addition the selection of method therefor and remaining condition with the phase of embodiment 1
Together, chitin 0.1770g is obtained, the protein regenerated is 0.090g.
Embodiment 5
Difference from Example 1 is that step (2) described regenerated solvent uses water, in addition used
The selection of method and remaining condition is same as Example 1, obtains chitin 0.1770g, the egg regenerated
White matter is 0.050g.
Embodiment 6
Difference from Example 1 is that step (2) described ionic liquid is choline glycine ([Cho] [Gly])
Ionic liquid, in addition the selection of method therefor and remaining condition is same as Example 1, obtains first
Shell quality amount is 0.1720g.
Embodiment 7
Difference from Example 1 is that step (2) described ionic liquid is choline serine ([Cho] [Ser])
Ionic liquid, in addition the selection of method therefor and remaining condition is same as Example 1, obtains first
Shell quality amount is 0.1550g.
Embodiment 8
Difference from Example 1 is that step (2) described ionic liquid is choline aspartic acid
([Cho] [Asp) ionic liquid, in addition the selection of method therefor and remaining condition with the phase of embodiment 1
Together, chitin quality is obtained for 0.1490g.
Embodiment 9
Difference from Example 1 is that step (2) described ionic liquid is choline leucine ([Cho] [Leu])
Ionic liquid, in addition the selection of method therefor and remaining condition is same as Example 1, obtains first
Shell quality amount is 0.1400g.
Embodiment 10
Difference from Example 1 is, step (2) described ionic liquid is choline tryptophan ([Cho] [Trp)
Ionic liquid, in addition the selection of method therefor and remaining condition is same as Example 1, obtains first
Shell quality amount is 0.1310g.
Embodiment 11
Difference from Example 1 is that step (2) described ionic liquid is choline alanine ([Cho] [Ala])
Ionic liquid 2.5g dissolve deliming shrimp shell, in addition the selection of method therefor and remaining condition with implementation
Example 1 is identical, obtains chitin quality for 0.1502g.Ionic liquid after filtering regenerates albumen using ethanol
Matter 0.1080g.
Comparative example 1
In the comparative example, using citric acid prawn shell carry out a deliming, separation and Extraction chitin it is specific
Step is as follows：
(1) the new fresh shrimp shell that 0.500g is dried is put into 100mL beakers, adds 10% citric acid
Solution 5g, is reacted 4 hours, and deliming shrimp shell is obtained after filtering.0.010g citric acids are added in filtrate after filtering
Calcium crystal seed, separates out 0.1080g calcium citrates, shrimp shell deliming rate is between 95-99% after 10 hours.
(2) deliming shrimp shell is dissolved using choline alanine ([Cho] [Ala]) ionic liquid 5g, is stirred at 110 DEG C
Mix 4 hours.Reaction terminates, and chitin 0.1755g is obtained after the filter residue and drying of filtering.Ionic liquid after filtering
Body regenerates protein 0.1108g using ethanol, is spin-dried for after ethanol, and ionic liquid supplements 2g every time, can continue
Recycle.
Comparative example 2
Two step delimings are carried out without using citric acid prawn shell in the comparative example, but directly using 1- ethyls -3-
([Emim] [OAc] ionic liquid 10g dissolves shrimp shell 0.5g to N-Methylimidazoleacetic salt, and 4 are stirred at 110 DEG C
Hour.Reaction terminates, and centrifuges to obtain insoluble matter 0.26g, and supernatant ethanol regenerates to obtain regrowth 0.15g, analysis
Calcium carbonate content 46% in insoluble matter and regrowth composition, insoluble matter, protein 43%, chitin 11%,
Calcium carbonate content 28% in regrowth, protein content 18%, chitin 54%.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention by above-described embodiment
Above-mentioned method detailed is not limited to, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.
Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to each original of product of the present invention
The equivalence replacement of material and the addition of auxiliary element, the selection of concrete mode etc., all fall within the protection model of the present invention
Within the scope of enclosing and disclosing.
Claims (10)
1. a kind of separating and extracting process of chitin, it is characterised in that the described method comprises the following steps：
(1) remove the calcium in shrimp and crab shells using the step deliming method of citric acid two and obtain deliming shrimp and crab shells；
(2) protein in degradable ion liquid dissolving deliming shrimp and crab shells, isolated chitin are utilized.
2. according to the method described in claim 1, it is characterised in that step (1) step of citric acid two
Deliming method comprises the following steps：
A, using citric acid solution dissolve shrimp and crab shells, be filtrated to get a deliming shrimp and crab shells and a citric acid
Filtrate；
B, using citric acid solution dissolve a deliming shrimp and crab shells, be filtrated to get secondary deliming shrimp and crab shells and secondary
Citric acid filtrate；
C, respectively the addition calcium citrate crystal seed into a citric acid filtrate and secondary citric acid filtrate, stand analysis
Go out calcium citrate.
3. method according to claim 2, it is characterised in that citric acid solution described in step A
Mass percent concentration is 8-15%；
Preferably, citric acid solution described in step A and shrimp shell mass ratio are 5-8:1；
Preferably, the time of citric acid solution dissolving shrimp and crab shells is 2-4 hours described in step A；
Preferably, temperature when being dissolved described in step A is 10-30 DEG C.
4. according to the method in claim 2 or 3, it is characterised in that citric acid solution described in step B
Mass percent concentration be 4-10%；
Preferably, citric acid solution described in step B and a deliming shrimp and crab shells mass ratio are 4-6:1；
Preferably, the time that a deliming shrimp and crab shells are dissolved described in step B is 1-3 hours；
Preferably, temperature when being dissolved described in step B is 10-30 DEG C.
5. the method according to any one of claim 2-4, it is characterised in that lemon described in step C
The addition of sour calcium crystal seed is the 1-5% of the theoretical amount of precipitation of calcium citrate；
Preferably, step A and step B is supplemented into the citric acid solution after precipitation calcium citrate described in step C
The 25-35% Posterior circles of the citric acid total amount used are used.
6. the method according to any one of claim 1-5, it is characterised in that step (2) is described
Degradable ionic liquid is choline amino acid ion liquid；
Preferably, step (2) the degradable ionic liquid is choline glycine ionic liquid, the ammonia of choline third
Acid ion liquid, choline leucine ionic liquid, choline serine ionic liquid, choline lysine ionic liquid
Body, choline ionotropic glutamate liquid, choline aspartic acid ionic liquid, choline phenylalanine ionic liquid,
Choline tryptophan ionic liquid, choline isoleucine ionic liquid, choline threonine ionic liquid, choline figured silk fabrics
Propylhomoserin ionic liquid, choline arginine ionic liquid, choline histidine ionic liquid, choline paddy amic acid from
Sub- liquid, choline proline ionic liquid, choline methionine ionic liquid or choline N acid ion
In liquid any one or at least two combination.
7. the method according to any one of claim 1-6, it is characterised in that step (2) is described
The mass ratio of degradable ionic liquid and deliming shrimp and crab shells is 5-20:1.
8. the method according to any one of claim 1-7, it is characterised in that step (2) is described
It it is 80-130 DEG C using the temperature of the protein in degradable ion liquid dissolving deliming shrimp and crab shells；
Preferably, step (2) protein using in degradable ion liquid dissolving deliming shrimp and crab shells
Time is 4-6 hours.
9. the method according to any one of claim 1-8, it is characterised in that step (2) is described
It is separated into and is separated by filtration；
Preferably, protein utilization regeneration is molten in the shrimp and crab shells dissolved in step (2) in degradable ionic liquid
Agent regenerates protein；
Preferably, the regenerated solvent is water and/or ethanol；
Preferably, regenerate after the degradable ionic liquid after protein separates with regenerated solvent, to degradable
The 10-20% Posterior circles that step (2) described degradable ionic liquid usage amount is supplemented in ionic liquid are used.
10. the method according to any one of claim 1-9, it is characterised in that methods described includes
Following steps：
(1) using mass percent concentration for 8-15% citric acid solution in dissolving shrimp and crab shells at 10-30 DEG C
2-4 hours, the citric acid solution was 5-8 with shrimp shell mass ratio:1, be filtrated to get deliming shrimp and crab shells and
Citric acid filtrate；Using the citric acid solution that mass percent concentration is 4-10% in dissolving at 10-30 DEG C
Deliming shrimp and crab shells 1-3 hours, the citric acid solution and a deliming shrimp and crab shells mass ratio are 4-6:1,
It is filtrated to get secondary deliming shrimp and crab shells and secondary citric acid filtrate；Respectively to a citric acid filtrate and secondary lemon
The 1-5% of the theoretical amount of precipitation of calcium citrate calcium citrate crystal seed is incorporated as in lemon acidleach liquid, stands and separates out lemon
Sour calcium, obtains deliming shrimp and crab shells；
(2) it is small in dissolving the protein 4-6 in deliming shrimp and crab shells at 80-130 DEG C using degradable ionic liquid
When, the mass ratio of the degradable ionic liquid and deliming shrimp and crab shells is 5-20:1, it is separated by filtration and obtains crust
Element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265885.7A CN107312109A (en) | 2016-04-26 | 2016-04-26 | Chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265885.7A CN107312109A (en) | 2016-04-26 | 2016-04-26 | Chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107312109A true CN107312109A (en) | 2017-11-03 |
Family
ID=60185586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610265885.7A Pending CN107312109A (en) | 2016-04-26 | 2016-04-26 | Chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107312109A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109260759A (en) * | 2018-09-29 | 2019-01-25 | 中国科学院过程工程研究所 | A kind of method of choline hydrophobic ionic liquid extraction and separation glycine |
| CN109265201A (en) * | 2018-11-21 | 2019-01-25 | 山东农业大学 | Using animal wool lysate as the bio-feritlizer of effective component and preparation method and application |
| CN109293795A (en) * | 2018-08-30 | 2019-02-01 | 佛山科学技术学院 | A kind of nano-chitosan material and its preparation method and application |
| WO2024031186A1 (en) * | 2022-08-08 | 2024-02-15 | Neptune Nanotechnologies Inc. | Solvent systems and methods for processing chitin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260051A (en) * | 2008-04-24 | 2008-09-10 | 中国科学院过程工程研究所 | Biodegradable choline-like ionic liquid |
| CN101407832A (en) * | 2008-11-05 | 2009-04-15 | 泰祥集团技术开发有限公司 | Method for producing chitin, calcium citrate and protein powder |
| CN101659711A (en) * | 2009-09-04 | 2010-03-03 | 扬州鸿信生物制品有限公司 | Technology for extracting chitin from shrimp and crab shells |
| CN102161714A (en) * | 2011-01-28 | 2011-08-24 | 上海海洋大学 | Process for preparing chitosan and calcium citrate |
| CN102964467A (en) * | 2011-09-01 | 2013-03-13 | 湛江师范学院 | New process for preparing chitin |
| CN105146047A (en) * | 2015-10-19 | 2015-12-16 | 内蒙古清谷新禾有机食品集团有限责任公司 | Method for extracting buckwheat protein from buckwheat |
-
2016
- 2016-04-26 CN CN201610265885.7A patent/CN107312109A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260051A (en) * | 2008-04-24 | 2008-09-10 | 中国科学院过程工程研究所 | Biodegradable choline-like ionic liquid |
| CN101407832A (en) * | 2008-11-05 | 2009-04-15 | 泰祥集团技术开发有限公司 | Method for producing chitin, calcium citrate and protein powder |
| CN101659711A (en) * | 2009-09-04 | 2010-03-03 | 扬州鸿信生物制品有限公司 | Technology for extracting chitin from shrimp and crab shells |
| CN102161714A (en) * | 2011-01-28 | 2011-08-24 | 上海海洋大学 | Process for preparing chitosan and calcium citrate |
| CN102964467A (en) * | 2011-09-01 | 2013-03-13 | 湛江师范学院 | New process for preparing chitin |
| CN105146047A (en) * | 2015-10-19 | 2015-12-16 | 内蒙古清谷新禾有机食品集团有限责任公司 | Method for extracting buckwheat protein from buckwheat |
Non-Patent Citations (3)
| Title |
|---|
| 于文国等: "《生物分离技术 第2版》", 30 June 2010, 化学工业出版社 * |
| 张亚: "《离子液体的应用及研究》", 31 October 2009, 陕西科学技术出版社 * |
| 黄亚东: "《发酵调味品生产技术》", 30 June 2014, 中国轻工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293795A (en) * | 2018-08-30 | 2019-02-01 | 佛山科学技术学院 | A kind of nano-chitosan material and its preparation method and application |
| CN109260759A (en) * | 2018-09-29 | 2019-01-25 | 中国科学院过程工程研究所 | A kind of method of choline hydrophobic ionic liquid extraction and separation glycine |
| CN109265201A (en) * | 2018-11-21 | 2019-01-25 | 山东农业大学 | Using animal wool lysate as the bio-feritlizer of effective component and preparation method and application |
| WO2024031186A1 (en) * | 2022-08-08 | 2024-02-15 | Neptune Nanotechnologies Inc. | Solvent systems and methods for processing chitin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103613637A (en) | Method of preparing proteins, chitin and chitosan from degreased shrimp meals of euphausia superba | |
| CN107312109A (en) | Chitin separating and extracting process in a kind of shrimp and crab shells based on degradable ionic liquid | |
| CN100398566C (en) | Environment-protection low-consumption process for preparing chitin from shrimp shell and for extracting bioactivity substance | |
| CN103467624B (en) | A kind of extracting method of heparin sodium crude | |
| CN104140474B (en) | A kind of method of utility in comprehensive utilizing shrimp Eriocheir sinensis skin | |
| CN103589507B (en) | Process for extracting krill oil, co-produced protein and chellotosan from antarctic krill powder | |
| CN106866842A (en) | Using ionic liquid chitin, protein and calcium of organic acid method are prepared from shrimp shell | |
| CN108866134B (en) | Preparation method of silkworm pupa protein polypeptide chelated calcium | |
| CN102643368A (en) | Method for synchronously extracting taurine, chitin and polypeptide from shrimp heads and shrimp leftovers | |
| CN102766524A (en) | Method for squeezing edible tea seed oil at normal temperature | |
| CN105249464A (en) | Preparation method of shrimp peptides chelated calcium | |
| CN108935919A (en) | A kind of production technology of anti-oxidant rice protein powder | |
| CN105876660A (en) | Method for preparing yak-sheep bone powder by utilizing enzyme method | |
| CN102161714A (en) | Process for preparing chitosan and calcium citrate | |
| CN103483182B (en) | Method for comprehensively utilizing procambarus clarkia by-products | |
| CN104592417A (en) | Enzyme-process extraction technology for chitin | |
| CN102732592A (en) | Method for preparing freshwater fish bone gelatin by enzyme process | |
| CN102675082B (en) | Preparation method of calcium propionate by egg shell | |
| CN102726599B (en) | Preparation process for novel bone meal | |
| CN103848929A (en) | Process for high-efficiently extracting sodium heparin | |
| CN109280096A (en) | A kind of method of comprehensive utilization of shrimp and crab shells | |
| CN107494886A (en) | A kind of albumen powder product using the molten slurry production of fish | |
| CN103224971B (en) | Fish skin collagen deodorizing production method | |
| CN1125875C (en) | Cotton oil extracting and detoxicating process | |
| CN102150875B (en) | Enzymolysis method for bone dregs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171103 |