CN104788584A - New technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials - Google Patents
New technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials Download PDFInfo
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- CN104788584A CN104788584A CN201410024693.8A CN201410024693A CN104788584A CN 104788584 A CN104788584 A CN 104788584A CN 201410024693 A CN201410024693 A CN 201410024693A CN 104788584 A CN104788584 A CN 104788584A
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Abstract
The invention relates to a new technology for clean production of chitosan and carboxymethyl chitosan by using crustacean shell raw materials. The method comprises the following steps: crushing shrimp shells, crab shells and other crustacean shell raw materials, directly reacting in an alcohol, alkali and water mixed system without calcium or protein removal, washing, and filtering to obtain calcium carbonate-containing crude chitosan for direct use; or directly adding chloroacetic acid, carrying out a chitosan carboxymethylation one-pot boiling reaction, washing a solid obtained after the reaction, filtering, drying to obtain a crude carboxymethyl chitosan and calcium carbonate mixture for direct use, or adding water to dissolve the mixture to obtain separated calcium carbonate which can be used a filler and a solution which can be used as a product directly or after concentration drying, and carrying out alcohol precipitation to obtain pure carboxymethyl chitosan. The above crude or pure product can be widely used in the fields of papermaking, binders, coatings and sustained and controlled release fertilizers. A washed filtrate contains amino acids and small peptides, and can be used as an animal amino acid fertilizer raw material or plant amino acid fertilizer or microbial nitrogen source nutriment after solvent concentration recovery.
Description
Technical field
Patent of the present invention relates to a kind of crustaceans raw material cleaner production chitosan and cm-chitosan novel process, belongs to biomass economy and natural product technical field of modification.
Background technology
Chitin (chitin) earth is only second to cellulosic second largest renewable resources, extensively be present in the cell walls of arthropods, mollusk, annelid, protozoon and fungi and algae, crustacean crust such as its Prawn, crab etc. is rich in the chitin of 15%-35%, and annual chitin biosynthesizing amount is about more than 1,000 hundred million tons.The elementary cell of chitin is acetylglucosamine, and it is the polymkeric substance be formed by connecting by β-(1 → 4)-glycosidic link by 1000-3000 acetyl glucoseamin residues.Chitosan (chitosan) is the deacetylated product of chitin N-, is the nitrogenous alkaline polysaccharide that nature uniquely exists in a large number.Chitin is due in molecule and the existence of intermolecular hydrogen bonding, define macromolecular secondary structure, simultaneously due to the regularity of molecular structure, make chitin molecule easily form crystallization, thus make crustaceans have hard shell, be insoluble in water and organic solvent.Extracted and derivatize by the low cost of chitin, can the chitin development of resources of horn of plenty and the starting material guarantee increase new way of rare-view set-up.
Cm-chitosan is a kind of important water miscible chitin derivativ, has the effects such as thickening, bonding, film forming, moisture absorption, emulsification, can be used for the fields such as makeup, medicine, chemical industry, agricultural, papermaking.In paper pulp, such as add the effect that chitin derivativ auxiliary agent not only can obtain antibacterial, mildew-resistant, deodorizing, moisture absorption, but also can reach crease-resistant, antistatic, improve the function of intensity; Especially for process paper for daily use, paper can be made to have soft, plentiful, comfortable physical property.But because cm-chitosan there is no the industrial application technology and production marketing possessing economic and technical feasibility so far, therefore develop super quality and competitive price, environmental protection production cm-chitosan processing method valuable.
The existing method preparing cm-chitosan is raw material mainly with chitosan greatly, in organic solvent medium after alkalization, then carries out carboxymethylation reaction, or is that raw material carries out de-acetyl carboxymethylation again in alkali lye and organic solvent mixing solutions with chitin.The main drawback of these methods is:
1) extraction cost of raw material chitin is high, have employed the decalcification of shrimp shell crab shell diluted acid, then through 5% ~ 8% alkali lye high cooking deproteinated technique, not only soda acid and energy consumption are large, and cause Heavy environmental pollution.
2) easily cause degradation of chitin in acid treatment process, waste valuable biological calcium resource.
3) chitosan is with chitin deacetylation in the high alkali liquid of 40 ~ 50%, need obtain through being separated, washing.And also need low temperature to alkalize when preparing cm-chitosan, and not only complex process, and alkaline consumption, energy consumption, wastewater flow rate are large.
4) full price that existing chitin and derivative production technique thereof fail to realize the crustaceans resources such as shrimp and crab shells utilizes, cause biological calcium, protein resource waste and serious environmental pollution, cause production cost high, valuable product, constrains the exploitation of abundant crustaceans resource.
Summary of the invention
Crustaceans raw material main component is calcium carbonate, protein and chitin, it is all take to use acid dissolve calcium carbonate that existing chitin extracts, and the Deproteinated extracting mode of alkali, causes acid and alkali consumption amount large, albumen, biological calcium are difficult to utilize, and also can cause degradation of chitin simultaneously.Therefore propose in alcohol ~ alkali ~ aqueous systems " one kettle way " to carry out derivative materialization to chitin and prepare chitosan or cm-chitosan, utilize calcium carbonate and protein resource simultaneously.
For achieving the above object, the present invention takes following technical scheme: by crustaceans raw material pulverizing, in alcohol ~ alkali ~ water mixed system, make chitin deacetylase base become chitosan, make proteolytic degradation become amino acid, little peptide simultaneously, then the solid after having reacted can be added water washing, filter and obtain chitosan, calcium carbonate mixture; Also can directly add Mono Chloro Acetic Acid after completion of the reaction and carboxymethylation is carried out to chitosan wherein, obtain cm-chitosan.Scheme comprises the steps:
1) to be ground into 30 ~ 300 object powder for subsequent use for shrimp and crab shells solid drying.
2) solid alkali is added in alcohol water mixed system, stir and form white paste liquid, then a certain amount of powder is claimed to join in above-mentioned mixed solution, under heated and stirred, the fully de-acetyl of chitin, albumen is fully hydrolyzed, after having reacted can by solids wash, filter to obtain chitosan, calcium carbonate mixture, filtrate reclaims the material such as amino acid, little peptide; Also next step reaction can directly be carried out.
3), after the fully de-acetyl of chitin completes, divide in system and add Monochloro Acetic Acid 3 ~ 7 times, under heating, carry out the carboxymethylation reaction of chitosan.
4) product 70% ethanolic soln washs 3 times, and filtrate reclaims the material such as amino acid, little peptide, and solvent cycle utilizes.Solid drying obtains cm-chitosan and calcium carbonate mixture directly uses, or the mixture product separation that can be dissolved in water goes out precipitation of calcium carbonate, the cm-chitosan that the aqueous solution can directly use or alcohol is analysed purer.
The result of process optimization shows: alcohol selects Virahol, ethanol, propyl carbinol etc., and alkali selects the highly basic such as sodium hydroxide, potassium hydroxide.De-acetyl chitin temperature of reaction is room temperature ~ boiling temperature, and the reaction times is 1 ~ 12h; Carboxymethylation reaction temperature is room temperature ~ 70 DEG C, and the reaction times is 0.5 ~ 12h.The mass ratio of alcohol and raw material (containing 15% chitin) is 1 ~ 5: 1, and the mass ratio of water and raw material is 0.1 ~ 0.5: 1, and the mass ratio of alkali and raw material is 0.2 ~ 0.5: 1; In carboxymethylation reaction, the mass ratio of Monochloro Acetic Acid and raw material is 0.1 ~ 0.5: 1.
The present invention reacts in alcohol ~ alkali ~ water mixed system, because alcohol molecule only has a reactive hydrogen with the larger hydrophobic group of volume, therefore alcohol system hydrogen bond and to OH
-solvation much more weak than water, OH
-alkalescence and nucleophilicity larger than aqueous systems; this system realizes penetrating and attack fine and close crust surface crystallization district; overcome " shielding " effect; strengthen nucleophilie nucleus ability to acyl group, realize the short period, be degraded into the reaction that amino acid and little peptide and chitin deacetylase prepares chitosan compared with albumen under low alkaline concentration, lesser temps.Simultaneously chitosan can abundant swelling alkalization in organic system and highly basic body, infiltrates and carboxymethylation reaction creates condition for Monochloro Acetic Acid molecules of salt, can improve Monochloro Acetic Acid transformation efficiency, realize " treating different things alike " and react.
The protein hydrolyzate that filtering separation obtains, through concentration and recovery amino acid, little peptide (see accompanying drawing 2), solvent cycle is applied mechanically simultaneously.Amino acid, little peptide can be used for vegetable fertilizer, microbial nutrition source, marine organisms fodder additives etc., and in crustaceans resource, valuable protein resource obtains utilization.Biological calcium carbonate can be used as product composition or raw material widespread use, chitosan or cm-chitosan crude product or the application of sterling in fields such as papermaking, binding agent, sustained-controll-release fertilisers.Novel process avoids a large amount of consumption of soda acid and the generation of waste water, achieves energy-saving and cost-reducing and cleaner production.
concrete implementation step
1 feedstock analysis and preparation
For subsequent use by being ground into 30-300 order in prawn shrimp shell, the content of basal component is: calcium carbonate 48%, chitin 15%, lipid and protein 37 %.
2 chitin deacetylases
Aqueous sodium hydroxide solution adds in Virahol and is configured to Virahol-alkali-aqueous systems, stir and form white slurry mixture, then a certain amount of powder is claimed to join in above-mentioned mixed solution, 3h is reacted under stirring, make the fully de-acetyl of chitin, albumen is fully degraded, and the experiment content that related process is optimized is as follows:
A: sodium hydroxide different amounts (m
(shrimp shell meal): m
(sodium hydroxide)=4: 1,3.5: 1,3: 1,2.5: 1) impact on chitin deacetylase effect
B: water content (5%, 10%, 15%, the 20%) impact on chitin deacetylase effect in system
C: the impact of differing temps (50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C) on chitin deacetylase effect
3 chitosan carboxymethylations
After above-mentioned reaction completes, directly divide in system and add Monochloro Acetic Acid 3 ~ 7 times, carry out carboxymethylation reaction 3h, related process experiment content is as follows:
A: Monochloro Acetic Acid different amounts (m
(shrimp shell meal): m
(-Mono Chloro Acetic Acid)=10: 1,8: 1,6: Isosorbide-5-Nitrae: 1) on the impact of chitosan carboxymethylation effect
B: the impact of differing temps (45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C) on chitosan carboxymethylation effect
4 product analyses
The related check of product and analytical procedure are see table one
Table one: product analysis project and analytical procedure
Embodiment
The present invention can be further described by embodiment hereinafter.Following embodiment reflects implementation result under different hydro sodium oxide, Monochloro Acetic Acid, temperature, water-content condition and the application implementation effect etc. of product in papermaking.
Embodiment 1
Sodium hydrate solid is added in isopropanol water mixed system; for some time formation liquid/paste is stirred at 60 DEG C; then another name shrimp shell meal end is divided to join in above-mentioned mixed solution; electric stirring 3h; the abundant deacetylation of chitin, solid adds water washing and obtains chitosan, calcium carbonate mixture, then dissolving with hydrochloric acid chitosan and calcium carbonate; ethanol is counter is settled out chitosan, obtains sterling chitosan with 70% alcohol solution repetitive scrubbing removing calcium chloride.Deacetylation is measured by acid base titration.Different m (shrimp shell meal): the related experiment result at m (sodium hydroxide), water content, temperature is see table two, table three, table four.
The amount of table two sodium hydroxide is on the impact of chitin deacetylase degree
Table three water content is on the impact of chitin deacetylase degree
Table four temperature is on the impact of chitin deacetylase degree
Embodiment 2
15g sodium hydrate solid is added respectively in containing the 100ml isopropanol water mixed system of 10% water; for some time formation liquid/paste is stirred at 60 DEG C; then divide another name 45g decalcification shrimp shell meal end to join in above-mentioned mixed solution, electric stirring 3h at 60 DEG C, after the abundant deacetylation of chitin.Divide 3 ~ 7 times again and add Monochloro Acetic Acid respectively, carboxymethylation 3h is carried out to chitosan.The solid that filtering separation obtains 70% ethanolic soln washs to obtain cm-chitosan, calcium carbonate mixture.Mixture is dissolved in water, and the centrifugal supernatant liquor obtained adds 5 times of volume alcohol settling, and then precipitates three times by 80% washing with alcohol, dry sterling cm-chitosan, the carboxylation degree of potentiometric determination product.Different m
(shrimp shell meal): m
(-Mono Chloro Acetic Acid), related experiment result at temperature is see table five, table six.
Table May Day, chloroacetic amount was on the impact of chitosan carboxylation degree
Table six temperature is on the impact of chitosan carboxylation degree
Embodiment 3
In the 100ml ethanol water mixed system containing 10% water, add 30g sodium hydrate solid stir, then claim 45g decalcification shrimp shell meal end to join in above-mentioned mixed solution, electric stirring backflow 3h at 80 DEG C, the abundant deacetylation of chitin.Divide 3 ~ 7 times again and add Monochloro Acetic Acid, carboxymethylation 3h is carried out to chitosan.The washing of product alcohol solution is dry obtains 28g mixture.Be dissolved in water and be settled out calcium carbonate 21g, solution with ethanol is counter precipitates to obtain cm-chitosan 6.8.g.The deacetylation of carboxymethyl chitosan sugar product is 0.72, carboxylation degree 0.69.
Embodiment 4
15g sodium hydrate solid is added respectively in containing the 100ml isopropanol water mixed system of 10% water; for some time formation liquid/paste is stirred at 60 DEG C; then claim 45g decalcification shrimp shell meal end to join in above-mentioned mixed solution, electric stirring 3h at 60 DEG C, after the abundant deacetylation of chitin.Divide 3 ~ 7 times again and add 7.5g Monochloro Acetic Acid, carboxymethylation 3h is carried out to chitosan.Product alcohol solution washs three times, dry cm-chitosan, calcium carbonate mixture 28.5g, yield (calculating by shrimp shell weight) 63.3%.Filtrate rotary evaporation removing alcohol solution, residue obtains 33.2g containing the solid vacuum-drying of the material such as amino acid, little peptide, and obtaining nitrogen content through ultimate analysis is 4%.Calcium carbonate, carboxymethyl chitosan sugar mixture are dissolved in water and are settled out calcium carbonate 21g, and calcium carbonate yield is 97%.Solution with ethanol is counter to be precipitated, dry cm-chitosan 7.5g, and yield be (by the calculation of chitin weight) 115%.
Embodiment 5
In paper pulp, add cm-chitosan (deacetylation is 0.82, and carboxylation degree is 0.89,2% viscosity is 453mPa.s) then carry out copy paper, measure the properties of paper, correlated results gathers as table seven.
Table seven cm-chitosan addition is on the impact of paper properties
Accompanying drawing illustrates:
The FT-IR spectrogram of accompanying drawing 1 chitin, chitosan, cm-chitosan
The 13C-NMR collection of illustrative plates of cm-chitosan waste fluid matter prepared by accompanying drawing 2
Claims (7)
1. a crustaceans raw material cleaner production chitosan and cm-chitosan novel process, key step is: by crustaceans raw material pulverizing to 30 ~ 300 order, in alcohol ~ alkali ~ water mixed system, make chitin deacetylase base become chitosan, make proteolytic degradation become amino acid, little peptide simultaneously, then the solid after having reacted can be added water washing, filter and obtain chitosan, calcium carbonate mixture; Also can directly add Mono Chloro Acetic Acid after completion of the reaction and carry out carboxymethylation to chitosan wherein, reacted solid obtains cm-chitosan, calcium carbonate mixture through washing, filtration.
2. the method for claim 1, is characterized in that: crustaceans raw material can be the Crustacean shell such as shrimp, crab shell, and alcohol can select Virahol, ethanol, propyl carbinol etc., and alkali can select the highly basic such as sodium hydroxide, potassium hydroxide.
3. the method for claim 1, in alcohol-alkali-aqueous systems, de-acetyl chitin temperature of reaction is room temperature ~ boiling temperature, and the reaction times is 1 ~ 12h; Carboxymethylation reaction temperature is room temperature ~ 70 DEG C, and the reaction times is 0.5 ~ 12h.
4. the method for claim 1, the mass ratio of alcohol and raw material is 1 ~ 5: 1, and the mass ratio of water and raw material is 0.1 ~ 0.5: 1, and the mass ratio of alkali and raw material is 0.2 ~ 0.5: 1; In carboxymethylation reaction, the mass ratio of Monochloro Acetic Acid and raw material is 0.1 ~ 0.5: 1, and Monochloro Acetic Acid adds in batches.
5. the method for claim 1, is characterized in that: cm-chitosan, the calcium carbonate mixture product separation that can be dissolved in water goes out precipitation of calcium carbonate, the cm-chitosan that the aqueous solution can directly use or alcohol is analysed purer.
6. the method for claim 1, the protein hydrolyzate that filtering separation obtains, through concentration and recovery amino acid, little peptide, solvent cycle is applied mechanically simultaneously.
7. use the serial chitosan that obtains of above-mentioned method or cm-chitosan crude product or sterling also to belong to this right in the application in the fields such as papermaking, binding agent, sustained-controll-release fertiliser.
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| CN106581039A (en) * | 2016-11-02 | 2017-04-26 | 上海陶盛生物技术有限公司 | Applications of carboxymethyl chitosan to preparation or screening of products for antiallergic treatment |
| CN107096508A (en) * | 2017-06-28 | 2017-08-29 | 江西省农业科学院土壤肥料与资源环境研究所 | A kind of modification biological crust heavy metal absorbent and preparation method and application |
| CN107722138A (en) * | 2017-07-31 | 2018-02-23 | 山东人文置业有限公司 | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan |
| CN107892371A (en) * | 2017-10-12 | 2018-04-10 | 广州振清环保技术有限公司 | A kind of polysilics acid metal salt and modification of chitosan compound coagulant and preparation method thereof |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
| CN109796542A (en) * | 2018-12-25 | 2019-05-24 | 华中科技大学 | A kind of shell-fish solid waste recycling system and method |
| CN109966505A (en) * | 2019-03-29 | 2019-07-05 | 厦门大学 | A kind of natural sustained and controlled release carrier material of nano-pore channel type and preparation method |
| CN110054912A (en) * | 2019-04-10 | 2019-07-26 | 华中科技大学 | A kind of method and product being pyrolyzed preparation high level gum filler based on shrimp crab based shell |
| CN110563860A (en) * | 2019-10-25 | 2019-12-13 | 石家庄亿生堂医用品有限公司 | preparation method of carboxymethyl chitosan |
| CN112375159A (en) * | 2020-11-13 | 2021-02-19 | 浙江万里学院 | Method for preparing chitosan by comprehensively treating shrimp and crab shells |
| CN112891369A (en) * | 2021-04-09 | 2021-06-04 | 厦门大学 | Potassium chloride sustained-release tablet prepared by taking crab shell powder and derivative product thereof as auxiliary materials and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106581039A (en) * | 2016-11-02 | 2017-04-26 | 上海陶盛生物技术有限公司 | Applications of carboxymethyl chitosan to preparation or screening of products for antiallergic treatment |
| CN107096508A (en) * | 2017-06-28 | 2017-08-29 | 江西省农业科学院土壤肥料与资源环境研究所 | A kind of modification biological crust heavy metal absorbent and preparation method and application |
| CN107096508B (en) * | 2017-06-28 | 2019-12-06 | 江西省农业科学院土壤肥料与资源环境研究所 | Modified biological crusta heavy metal adsorbent and preparation method and application thereof |
| CN107722138A (en) * | 2017-07-31 | 2018-02-23 | 山东人文置业有限公司 | A kind of chitin prepares the new method of water-soluble carboxymethyl chitosan |
| CN107892371B (en) * | 2017-10-12 | 2020-11-13 | 广州振清环保技术有限公司 | Polysilicate metal and modified chitosan composite coagulant and preparation method thereof |
| CN107892371A (en) * | 2017-10-12 | 2018-04-10 | 广州振清环保技术有限公司 | A kind of polysilics acid metal salt and modification of chitosan compound coagulant and preparation method thereof |
| CN108940373A (en) * | 2018-07-16 | 2018-12-07 | 广东石油化工学院 | Based on shrimp, the organic reaction catalyst of crab waste and the preparation method and application thereof |
| CN108940373B (en) * | 2018-07-16 | 2021-07-09 | 广东石油化工学院 | Organic reaction catalyst based on shrimp and crab wastes and preparation method and application thereof |
| CN109796542A (en) * | 2018-12-25 | 2019-05-24 | 华中科技大学 | A kind of shell-fish solid waste recycling system and method |
| CN109966505A (en) * | 2019-03-29 | 2019-07-05 | 厦门大学 | A kind of natural sustained and controlled release carrier material of nano-pore channel type and preparation method |
| WO2020199349A1 (en) * | 2019-03-29 | 2020-10-08 | 厦门大学 | Nano pore channel-type natural slow and controlled release carrier material and preparation method therefor |
| CN110054912A (en) * | 2019-04-10 | 2019-07-26 | 华中科技大学 | A kind of method and product being pyrolyzed preparation high level gum filler based on shrimp crab based shell |
| CN110563860A (en) * | 2019-10-25 | 2019-12-13 | 石家庄亿生堂医用品有限公司 | preparation method of carboxymethyl chitosan |
| CN112375159A (en) * | 2020-11-13 | 2021-02-19 | 浙江万里学院 | Method for preparing chitosan by comprehensively treating shrimp and crab shells |
| CN112891369A (en) * | 2021-04-09 | 2021-06-04 | 厦门大学 | Potassium chloride sustained-release tablet prepared by taking crab shell powder and derivative product thereof as auxiliary materials and preparation method |
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