CN103665191A - Preparation method of chitosan and immersion device for preparing chitosan - Google Patents
Preparation method of chitosan and immersion device for preparing chitosan Download PDFInfo
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- CN103665191A CN103665191A CN201310726179.4A CN201310726179A CN103665191A CN 103665191 A CN103665191 A CN 103665191A CN 201310726179 A CN201310726179 A CN 201310726179A CN 103665191 A CN103665191 A CN 103665191A
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Abstract
The invention relates to a preparation method of chitosan, which comprises the following steps of: screening, purifying, dicing, washing and drying shrimp shells and crab shells, soaking with an appropriate amount of hydrochloric acid for 5-8h, after filtering, recovering a calcium chloride solution, collecting the preliminarily decalcified shrimp shells and crab shells, soaking with excessive hydrochloric acid, collecting the decalcified shrimp shells and crab shells, boiling with a sodium hydroxide solution, cooling, then filtering, recovering the sodium hydroxide solution after filtration, obtaining the shrimp shells and crab shells having protein removed, removing water, soaking with potassium permanganate, soaking a filtration product in a reducer solution after filtration till complete decoloration, washing with water, drying to form chitin, soaking the chitin with sodium hydroxide for 15-20 h at 80-100 DEG C, cooling, filtering, cleaning a filtration product, removing residual sodium hydroxide, drying, and grinding to form the chitosan. The preparation method realizes high resource utilization rate, low production cost and low environmental pollution by recycling materials.
Description
Technical field
The present invention relates to a kind of preparation method of polymer glycan, be specifically related to a kind of preparation method of chitosan and prepare the liquid-immersion device of chitosan.
Background technology
The arthropodan shell such as shrimp, crab, also claims crust, is one of organic resource the abundantest on the earth, is on the earth, to be only second to cellulosic organic compounds containing nitrogen.China marine site is vast, and crustaceans resource is very abundant, and utilizable quantity is also considerable.In the last few years, along with the increase of fresh water and seawater shrimps, crab cultured output, have every year a large amount of shrimps, crab shell to produce, only waste-shrimp the shell in prawn processing, just has more than 10,000 ton.These a large amount of shrimps, crab shell byproduct, the overwhelming majority is thrown away, and causes the wasting of resources, environmental pollution.In shrimp, crab shell, not only contain a large amount of inorganic salt, main chemical compositions is calcium carbonate, magnesiumcarbonate, calcium phosphate, and the lead, mercury, manganese, arsenic, iron of trace etc., also contains a large amount of protein.In recent years, many countries are very fast for the research and utilization development of crustaceans resource, and research and the application of especially crustaceans resource being produced to chitin and chitosan, chitooligosaccharide-have extraordinary development.Along with the progress of chitin, chitosan, chitooligosaccharide-, have been found that it has purposes very widely in modern production life, is having irreplaceable effect aspect medicine, food, weaving, agricultural, environment etc.
The method of utilizing shrimp and crab shells to prepare chitosan is mainly chemical method, and its technical process comprises acidleach desalination, soda boiling deproteinated, oxidative decoloration, concentrated base deacetylation.But current technical process is difficult to obtain chitosan high deacetylized, high molecular simultaneously, and cost is high, seriously polluted.As Chinese patent application file (publication number: the preparation method who CN101974104A) discloses a kind of chitosan, the method comprises the pre-treatment of shrimp shell, the excessive hydrochloric acid that is 5-15% by mass concentration soaked after 4-6 hour, the sodium hydroxide alkaline purification 1-2 hour that is 10-20% by mass concentration, the potassium permanganate that is 2-5% by mass concentration again soaks 0.5-1 hour, filter, in the sodium sulfite solution that filtration product is 5-10% in mass concentration, soak 0.5-1 hour to obtain chitin, the sodium hydroxide solution that is finally 40-45% by chitin by excessive concentrations soaks 4-8 hour, obtain chitosan.In this preparation method, water consumption, energy consumption, acid consume, alkaline consumption is serious, and resource fails to fully utilize, and waste is serious, and environmental pollution is serious.
Summary of the invention
The object of the invention is to for above shortcomings in prior art, provides a kind of utilize resources synthetically, the preparation method of cost-saving chitosan.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of chitosan, and this preparation method comprises the following steps:
S1, by shrimp, crab shell through screening, removal of impurities, stripping and slicing, clean, dry;
S2, by the shrimp in step S1, appropriate salt acid soak 5-8 hour for crab shell, make calcium carbonate, calcium phosphate in shrimp, crab shell become calcium chloride with hydrochloric acid reaction, after filtration, calcium chloride is reclaimed, collect shrimp, crab shell after preliminary decalcification;
S3, by the shrimp of collecting in step S2, excessive salt acid soak for crab shell, be stirred in hydrochloric acid soln without bubble formation, reclaim unnecessary acid, collect shrimp, crab shell after decalcification;
S4, the shrimp of collecting in step S3, crab shell are boiled with sodium hydroxide solution, make protein dissolved, separated with chitin, by solution cooled and filtered, after filtering, reclaim sodium hydroxide solution, the shrimp of collecting, crab shell are through cleaning except shrimp, the crab shell of deproteinize;
S5, remove moisture after the shrimp in step S4, crab shell are cleaned, first with potassium permanganate, soak, refilter, after filtration, filtration product is dipped in reductant solution to decolouring completely, washing, the dry chitin that to obtain;
S6, by the chitin in step S5 at 80-100 ℃ with soaking with sodium hydroxide 15-20 hour, cooling, filter, cleaning and filtering product, removes remaining sodium hydroxide, dries, pulverizes and obtain chitosan;
Wherein, to the calcium chloride solution reclaiming in step S2, add appropriate sodium carbonate solution or pass into carbonic acid gas, after filtration, washing, after dry solid carbonic acid calcium;
In the sodium hydroxide solution reclaiming in step S4, add salt acid for adjusting pH to 5-6, after filtration, washing, after dry protein.
The present invention is according to the calcareous 70-80% that accounts in shrimp and crab shells, and protein accounts for 10-20%, and chitin accounts for basal component, character, the content of 5-10%, by chemical process, collects respectively calcium carbonate, protein, chitin, and is prepared into chitosan.In the preparation method of chitosan of the present invention, first shrimp and crab shells is removed to residual meat, cleaning can significantly reduce protein, grease enters in the soda boiling of postorder, can save acid, alkali, has also reduced the discharge of pollutent in rear program process.Pretreated shrimp and crab shells is first used appropriate salt acid soak, hydrochloric acid is now unnecessary acid solution recovery after step S3 pickling, and because now the amount of hydrochloric acid seldom, hydrochloric acid can total overall reaction, in the solution of getting rid of, only has calcium chloride, there is no spent acid, realize at Resource Recycling Utilization, free from environmental pollution when reducing costs.The present invention adopt preliminary pickling and again pickling be that preliminary decalcification and decalcification two steps are processed, so cyclical operation, has not only saved the consumption of hydrochloric acid, also the recovery of real hydrochloric acid, makes again last handling process be more prone to, and free from environmental pollution.Then the shrimp and crab shells after decalcification is boiled except deproteinize and grease with sodium hydroxide solution, during soda boiling, will constantly stir, protein is dissolved gradually, separated with chitin, grease is dissolved in alkali lye through soda boiling saponification, and unnecessary alkali lye sodium hydroxide solution can be used to extract protein after reclaiming.In addition, in the cleaning process of the present invention after pickling, alkali cleaning, first use seawater, then use fresh water, can fresh-water-saving 50%.Owing to containing astacin in shrimp and crab shells, in the process of pickling and soda boiling, do not destroy astacin completely, therefore, need to decolour by the shrimp and crab shells after to soda boiling with potassium permanganate, and make decolouring evenly with reductive agent.Finally chitin deacetylate is made to chitosan.The present invention is to react 15-20 hour in chitin being immersed in to sodium hydroxide at 80-100 ℃ in temperature.Temperature of reaction has impact to the time of the color and luster of chitosan and deacetylation.If temperature of reaction is too high, the shade deviation of chitosan, but the required reaction times is short, as reaction at 130-140 ℃, only needs within 1-2 hour, can purify ethanoyl, but the jaundice of the color and luster of chitosan.If temperature of reaction is 50-60 ℃, need just can purify ethanoyl in 24 hours, the color of chitosan is more shallow.When if temperature of reaction is 30 ℃, need within 130 hours, just can purify ethanoyl, and chitosan is pure white look.Therefore, the present invention, by lot of experiments, controls the temperature of reaction of deacetylation for 80-100 ℃, and the reaction times is 15-20 hour.In addition, in the preparation method of chitosan of the present invention, not only make chitosan, also from the calcium chloride solution being recovered to, make the solid carbonic acid calcium of food grade, from the sodium hydroxide solution being recovered to, make protein, realized the comprehensive utilization of resource.
In the preparation method of above-mentioned chitosan, the mass concentration of hydrochloric acid described in step S3 is 10-15%, and described soak time is 10-15 hour.
In the preparation method of above-mentioned chitosan, the mass concentration of sodium hydroxide described in step S4 is 8-10%, and described boiling temps is 80-90 ℃, boils while stirring as 2-3 hour.
In the preparation method of above-mentioned chitosan, the mass concentration of potassium permanganate described in step S5 is 1%, and soak time is 1-2 hour.
In the preparation method of above-mentioned chitosan, the reductive agent described in step S5 is one or more in Sulfothiorine, sodium bisulfite, oxalic acid, and the mass concentration of described reductive agent is 1-1.5%.
In the preparation method of above-mentioned chitosan, the mass concentration of sodium hydroxide described in step S6 is 40-50%.
Further preferably, in the preparation method of above-mentioned chitosan, also can further produce refining chitosan, by the above-mentioned chitosan making 10% acetate dissolution, remove by filter impurity, to dripping concentrated base 40% sodium hydroxide to solution in filtrate, be neutral, separate out the flocks of chitosan white, then use acetate dissolution, add excessive propanone, separate out the acetate of chitosan, filter, wash, dewater, be dried, obtain refining chitosan.Wherein, the mass concentration of described acetic acid is 8-12%.
Another object of the present invention is to provide a kind of as above-mentioned liquid-immersion device of preparing chitosan, this liquid-immersion device comprises that top has outer cylinder body and the inner barrel of opening, it is characterized in that, described outer cylinder body and inner barrel are cylindric, the external diameter of described inner barrel is less than the internal diameter of outer cylinder body, the height of inner barrel is less than the height of outer cylinder body, described inner barrel is connected on outer cylinder body by a demountable structure, the bottom of described inner barrel offers some liquid drain holes, on described outer cylinder body outer side wall, be connected with input duct, described input duct is connected for acid solution device with one, in input duct, be also provided with liquid inlet electromagnetic valve, described outer cylinder body bottom is connected with fluid pipeline, on fluid pipeline, be provided with liquid outlet electromagnetic valve, on the inwall of described outer cylinder body bottom, be fixed with pH value sensor, on the outer wall of described outer cylinder body, be fixed with controller, described pH value sensor, liquid outlet electromagnetic valve is all connected with this controller by circuit with liquid inlet electromagnetic valve.
The external diameter of inner barrel is less than the internal diameter of outer cylinder body, makes to have gap between the outer wall of inner barrel and the inwall of outer cylinder body, and inner barrel easily takes out in outer cylinder body.When prawn crab housing carries out pickling decalcification processing, first shrimp and crab shells body is put into inner barrel, now inner barrel is positioned at outer cylinder body, open liquid inlet electromagnetic valve, acid solution in confession acid solution device is in input duct flows into outer cylinder body, prawn crab housing fully soaks, and acid solution is closed liquid inlet electromagnetic valve after flowing into suitable amount; Along with the continuity of soak time, in immersion liquid, calcium chloride concentration increases gradually, and immersion liquid acidity reduces gradually, when pH value sensor detects immersion liquid when aobvious acid, just sends a signal to controller, and controller is controlled liquid outlet electromagnetic valve and opened, and immersion liquid is discharged from fluid pipeline.The acid detection of immersion liquid of this liquid-immersion device and the discharge process of immersion liquid are all to have controlled by controller, and level of automation is high, uses manpower and material resources sparingly, and has improved to a great extent production efficiency.The height of inner barrel is less than the height of outer cylinder body, make to there is certain difference of altitude between inner barrel bottom and outer cylinder body bottom, simultaneously inner barrel bottom has liquid drain hole, so shrimp and crab shells physical efficiency is soaked in immersion liquid completely, and the calcium salt in shrimp and crab shells body can fully be dissolved.
In the above-mentioned liquid-immersion device of preparing chitosan, on described outer cylinder body outer side wall, offer inlet opening, described input duct is connected with described inlet opening, described outer cylinder body bottom offers fluid hole, described fluid pipeline is connected with described fluid hole, and described fluid pipeline is connected with a collection box.After liquid outlet electromagnetic valve is opened, the immersion liquid in outer cylinder body flows in pipeline from fluid hole, then drains in collection box.
In the above-mentioned liquid-immersion device of preparing chitosan, described confession acid solution device comprises acid storing tank and water pump, the inlet pipe of described water pump is connected with acid storing tank, and the pipe that goes out of described water pump is connected with above-mentioned input duct, and water pump is connected with described controller by circuit.Water pump is extracted into the immersion liquid in acid storing tank in input duct and flows in outer cylinder body.Water pump is connected with controller and is made controller can control the work of water pump by circuit, improves level of automation.
In the above-mentioned liquid-immersion device of preparing chitosan, described demountable structure comprises hook one and hook two, and described hook one and hook two are separately fixed at the corresponding place, top of inner barrel, and hook one and hook two hanging supports are located on the top of outer cylinder body.
As another situation, in the above-mentioned liquid-immersion device of preparing chitosan, described demountable structure comprises steady brace one and steady brace two, described place, outer cylinder body top offers corresponding breach one and breach two, one end of described steady brace one is fixed on the outer wall on inner barrel top, the other end of steady brace one is placed in described breach one, and one end of described steady brace two is fixed on the outer wall on inner barrel top, and the other end of steady brace two is placed in described breach two.
In the above-mentioned liquid-immersion device of preparing chitosan, described controller is PLC programmable logic controller or singlechip controller.PLC programmable logic controller or singlechip controller all have higher control accuracy and operation stability.
Compared with prior art, tool of the present invention has the following advantages:
1, the present invention is by selecting the rational acid solution of mass concentration, alkali lye, potassium permanganate, reductive agent etc., by recycle, seawater is all first used in cleaning after pickling and soda boiling, then uses fresh water, both reduces production costs, save hydrochloric acid 30%, save alkali lye 20%, fresh-water-saving 50%, also can utilize resources synthetically, not only prepare chitosan, also can produce calcium carbonate, protein of food grade etc.
2, the present invention, by preliminary pickling and pickling again, has reduced the consumption of hydrochloric acid, makes again aftertreatment solution more, and free from environmental pollution.
3, the present invention, by selecting temperature of reaction and the reaction times of suitable deacetylation, makes to improve the color and luster of chitosan when guaranteeing deacetylation, makes deacetylation rate can reach 90%.
4, the height that the present invention prepares the inner barrel in the liquid-immersion device of chitosan is less than the height of outer cylinder body, make to there is certain difference of altitude between inner barrel bottom and outer cylinder body bottom, inner barrel bottom has liquid drain hole simultaneously, therefore shrimp and crab shells physical efficiency is soaked in immersion liquid completely, calcium salt in shrimp and crab shells body can fully be dissolved, can also make immersion liquid discharge clean, be more conducive to next step washing and caustic dip process simultaneously.
5, to prepare the level of automation of liquid-immersion device of chitosan high, easy to operate in this present invention.
Accompanying drawing explanation
Fig. 1 is the preparation method's of chitosan of the present invention schema.
Fig. 2 is the structural representation of apparatus of the present invention embodiment 4.
Fig. 3 is the sectional structure schematic diagram of apparatus of the present invention embodiment 4.
Fig. 4 is the structural representation of apparatus of the present invention embodiment 5.
Fig. 5 is the sectional structure schematic diagram of apparatus of the present invention embodiment 5.
In Fig. 2-5,1, outer cylinder body; 2, inner barrel; 3, liquid drain hole; 4, inlet opening; 5, liquid inlet electromagnetic valve; 6, fluid hole; 7, liquid outlet electromagnetic valve; 8, pH value sensor; 9, controller; 10, acid storing tank; 11, water pump; 12, hook one; 13, hook two; 14, steady brace one; 15, steady brace two; 16, breach one; 17, breach two; 18, collection box; 19, input duct; 20, fluid pipeline.
Specific embodiment
Be below specific embodiments of the invention, technical scheme of the present invention is further described, but the present invention is not limited to these embodiment.
The embodiment 1 for preparing chitosan
By shrimp, crab shell through screening, removal of impurities, stripping and slicing, clean, dry.
By appropriate salt acid soak 6 hours for above-mentioned shrimp, crab shell, make calcium carbonate, calcium phosphate in shrimp, crab shell become calcium chloride with hydrochloric acid reaction, after filtration, calcium chloride is reclaimed, collect shrimp, crab shell after preliminary decalcification; The calcium chloride solution obtaining to recovery adds appropriate sodium carbonate solution or passes into carbonic acid gas, and after filtration, washing, obtains solid carbonic acid calcium after being dried.
The salt acid soak that is 12% by excessive mass concentration by above-mentioned shrimp of collecting, crab shell 12 hours, is stirred in hydrochloric acid soln without bubble formation, collects shrimp, crab shell after decalcification.
The sodium hydroxide solution that is 9% by mass concentration by above-mentioned shrimp of collecting, crab shell at 85 ℃, boil while stirring into hour, make protein dissolved, separated with chitin, by solution cooled and filtered, after filtration, sodium hydroxide solution is reclaimed, collect shrimp, crab shell, must be except shrimp, the crab shell of deproteinize after cleaning; In the alkali lye sodium hydroxide solution obtaining to recovery, add salt acid for adjusting pH to 5.6, after filtration, washing, obtains protein after being dried.
The above-mentioned shrimp except deproteinize, crab shell are removed to moisture after cleaning, the potassium permanganate that is first 1% by mass concentration soaks 1 hour, refilter, in the reductive agent hypo solution that is 1.2% by filtration product in mass concentration after filtration, be dipped to decolouring complete, washing, the dry chitin that to obtain.
The soaking with sodium hydroxide that is 45% by mass concentration at 90 ℃ by the above-mentioned chitin making 18 hours, cooling, filter, cleaning and filtering product, removes remaining sodium hydroxide, dries, pulverizes and obtain chitosan.
By 10% acetate dissolution for the above-mentioned chitosan making, remove by filter impurity, to dripping mass concentration in filtrate, be that 40% sodium hydroxide to solution is neutral, separate out the flocks of chitosan white, use again acetate dissolution, add excessive propanone, separate out the acetate of chitosan, filter, wash, dewater, be dried, obtain refining chitosan.
The embodiment 2 for preparing chitosan
By shrimp, crab shell through screening, removal of impurities, stripping and slicing, clean, dry.
By appropriate salt acid soak 5 hours for above-mentioned shrimp, crab shell, make calcium carbonate, calcium phosphate in shrimp, crab shell become calcium chloride with hydrochloric acid reaction, after filtration, calcium chloride is reclaimed, collect shrimp, crab shell after preliminary decalcification; The calcium chloride solution obtaining to recovery adds appropriate sodium carbonate solution or passes into carbonic acid gas, and after filtration, washing, obtains solid carbonic acid calcium after being dried.
The salt acid soak that is 10% by excessive mass concentration by above-mentioned shrimp of collecting, crab shell 10 hours, is stirred in hydrochloric acid soln without bubble formation, collects shrimp, crab shell after decalcification.
It is 2 hours that the sodium hydroxide solution that is 8% by mass concentration by above-mentioned shrimp of collecting, crab shell boils while stirring at 80 ℃, make protein dissolved, separated with chitin, by solution cooled and filtered, after filtration, sodium hydroxide solution is reclaimed, collect shrimp, crab shell, must be except shrimp, the crab shell of deproteinize after cleaning; In the alkali lye sodium hydroxide solution obtaining to recovery, add salt acid for adjusting pH to 5, after filtration, washing, obtains protein after being dried.
The above-mentioned shrimp except deproteinize, crab shell are removed to moisture after cleaning, the potassium permanganate that is first 1% by mass concentration soaks 1 hour, refilter, in the reductant solution Sulfothiorine that is 1% by filtration product in mass concentration after filtration, sodium bisulfite, oxalic acid, be dipped to decolouring complete, washing, the dry chitin that to obtain.
The soaking with sodium hydroxide that is 40% by mass concentration at 80 ℃ by the above-mentioned chitin making 15 hours, cooling, filter, cleaning and filtering product, removes remaining sodium hydroxide, dries, pulverizes and obtain chitosan.
By 8% acetate dissolution for the above-mentioned chitosan making, remove by filter impurity, to dripping mass concentration in filtrate, be that 40% sodium hydroxide to solution is neutral, separate out the flocks of chitosan white, use again acetate dissolution, add excessive propanone, separate out the acetate of chitosan, filter, wash, dewater, be dried, obtain refining chitosan.
The embodiment 3 for preparing chitosan
By shrimp, crab shell through screening, removal of impurities, stripping and slicing, clean, dry.
By appropriate salt acid soak 8 hours for above-mentioned shrimp, crab shell, make calcium carbonate, calcium phosphate in shrimp, crab shell become calcium chloride with hydrochloric acid reaction, after filtration, calcium chloride is reclaimed, collect shrimp, crab shell after preliminary decalcification; The calcium chloride solution obtaining to recovery adds appropriate sodium carbonate solution or passes into carbonic acid gas, and after filtration, washing, obtains solid carbonic acid calcium after being dried.
The salt acid soak that is 15% by excessive mass concentration by above-mentioned shrimp of collecting, crab shell 15 hours, is stirred in hydrochloric acid soln without bubble formation, collects shrimp, crab shell after decalcification.
It is 3 hours that the sodium hydroxide solution that is 10% by mass concentration by above-mentioned shrimp of collecting, crab shell boils while stirring at 90 ℃, make protein dissolved, separated with chitin, by solution cooled and filtered, after filtration, sodium hydroxide solution is reclaimed, collect shrimp, crab shell, must be except shrimp, the crab shell of deproteinize after cleaning; In the alkali lye sodium hydroxide solution obtaining to recovery, add salt acid for adjusting pH to 6, after filtration, washing, obtains protein after being dried.
The above-mentioned shrimp except deproteinize, crab shell are removed to moisture after cleaning, the potassium permanganate that is first 1% by mass concentration soaks 2 hours, refilter, in the reductant solution Sulfothiorine that is 1.5% by filtration product in mass concentration after filtration, sodium bisulfite, oxalic acid, be dipped to decolouring complete, washing, the dry chitin that to obtain.
The soaking with sodium hydroxide that is 50% by mass concentration at 100 ℃ by the above-mentioned chitin making 20 hours, cooling, filter, cleaning and filtering product, removes remaining sodium hydroxide, dries, pulverizes and obtain chitosan.
By 12% acetate dissolution for the above-mentioned chitosan making, remove by filter impurity, to dripping mass concentration in filtrate, be that 40% sodium hydroxide to solution is neutral, separate out the flocks of chitosan white, use again acetate dissolution, add excessive propanone, separate out the acetate of chitosan, filter, wash, dewater, be dried, obtain refining chitosan.
A liquid-immersion device of preparing chitosan, comprises outer cylinder body 1, inner barrel 2, acid storing tank 10, water pump 11 and collection box 18 etc.
As shown in Figures 2 and 3, the top of outer cylinder body 1 and inner barrel 2 has opening, outer cylinder body 1 and inner barrel 2 are cylindric, the external diameter of inner barrel 2 is less than the internal diameter of outer cylinder body 1, the height of inner barrel 2 is less than the height of outer cylinder body 1, the top place corresponding at inner barrel 2 is fixed with respectively hook 1 and hook 2 13, and hook 1 and hook 2 13 hanging supports are at the place, top of outer cylinder body 1.The bottom of inner barrel 2 offers some liquid drain holes 3, on outer cylinder body 1 outer side wall, offer inlet opening 4 and be connected with input duct 19, one end of input duct 19 is connected with inlet opening 4, the other end of input duct 19 is connected with the pipe that goes out of water pump 11, the inlet pipe of water pump 11 is connected with acid storing tank 10, water pump 11 is connected with controller 9 by circuit, is provided with liquid inlet electromagnetic valve 5 in input duct 19.Outer cylinder body 1 bottom offers fluid hole 6, and the fluid pipeline 20 that fluid hole 6 and is arranged on outer cylinder body 1 bottom is connected, and is provided with liquid outlet electromagnetic valve 7 on fluid pipeline 20, and fluid pipeline 20 is connected with a collection box 18.After liquid outlet electromagnetic valve 7 is opened, the immersion liquid in outer cylinder body 1 flows in fluid pipeline 20 from fluid hole 6, then drains in collection box 18.On the inwall of outer cylinder body 1 bottom, be fixed with pH value sensor 8, be fixed with controller 9 on the outer wall of outer cylinder body 1, pH value sensor 8, liquid outlet electromagnetic valve 7 and liquid inlet electromagnetic valve 5 are all connected with this controller 9 by circuit.This controller 9 is PLC programmable logic controller or singlechip controller.
When prawn crab housing carries out pickling decalcification processing, first shrimp and crab shells body is put into inner barrel 2, now inner barrel 2 is positioned at outer cylinder body 1, open liquid inlet electromagnetic valve 5, for the immersion liquid in acid solution device, through inlet opening 4, flow in outer cylinder body 1, prawn crab housing fully soaks, and immersion liquid is closed liquid inlet electromagnetic valve 5 after flowing into suitable amount.Continuity along with soak time, in immersion liquid, calcium chloride concentration increases gradually, immersion liquid acidity reduces gradually, when pH value sensor 8 detects immersion liquid when aobvious acid, just send a signal to controller 9, between control inner barrel 2 bottoms and outer cylinder body 1 bottom, have certain difference of altitude, inner barrel 2 bottoms have liquid drain hole 3 simultaneously, therefore shrimp and crab shells physical efficiency is soaked in immersion liquid completely, and the calcium salt in shrimp and crab shells body can fully be dissolved.
The present embodiment with device embodiment 4 structure and principle basic identical, different place is: as shown in Figure 4 and Figure 5, inner barrel 2 be not by link up with 1 and hook 2 13 hanging supports on outer cylinder body 1.But by fixed locating stud 1 and steady brace 2 15 on inner barrel 2, at outer cylinder body, 1 place, top offers corresponding breach 1 and breach 2 17, wherein one end of steady brace 1 is fixed on the outer wall on inner barrel 2 tops, the other end of steady brace 1 is placed in breach 1, one end of steady brace 2 15 is fixed on the outer wall on inner barrel 2 tops, and the other end of steady brace 2 15 is placed in breach 2 17.
Although more used 1 herein, outer cylinder body; 2, inner barrel; 3, liquid drain hole; 4, inlet opening; 5, liquid inlet electromagnetic valve; 6, fluid hole; 7, liquid outlet electromagnetic valve; 8, pH value sensor; 9, controller; 10, acid storing tank; 11, water pump; 12, hook one; 13, hook two; 14, steady brace one; 15, steady brace two; 16, breach one; 17, breach two; 18, collection box; 19, input duct; 20, the term such as fluid pipeline, but do not get rid of the possibility of using other term.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or supplement or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made a detailed description and has quoted as proof some specific embodiments, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (10)
1. a preparation method for chitosan, is characterized in that, this preparation method comprises the following steps:
S1, by shrimp, crab shell through screening, removal of impurities, stripping and slicing, clean, dry;
S2, by the shrimp in step S1, appropriate salt acid soak 5-8 hour for crab shell, make calcium carbonate, calcium phosphate in shrimp, crab shell become calcium chloride with hydrochloric acid reaction, after filtration, calcium chloride is reclaimed, collect shrimp, crab shell after preliminary decalcification;
S3, by the shrimp of collecting in step S2, excessive salt acid soak for crab shell, be stirred in hydrochloric acid soln without bubble formation, reclaim unnecessary acid, collect shrimp, crab shell after decalcification;
S4, the shrimp of collecting in step S3, crab shell are boiled with sodium hydroxide solution, make protein dissolved, separated with chitin, by solution cooled and filtered, after filtering, reclaim sodium hydroxide solution, the shrimp of collecting, crab shell are through cleaning except shrimp, the crab shell of deproteinize;
S5, remove moisture after the shrimp in step S4, crab shell are cleaned, first with potassium permanganate, soak, refilter, after filtration, filtration product is dipped in reductant solution to decolouring completely, washing, the dry chitin that to obtain;
S6, by the chitin in step S5 at 80-100 ℃ with soaking with sodium hydroxide 15-20 hour, cooling, filter, cleaning and filtering product, removes remaining sodium hydroxide, dries, pulverizes and obtain chitosan;
Wherein, to the calcium chloride solution reclaiming in step S2, add sodium carbonate solution or pass into carbonic acid gas, after filtration, washing, after dry solid carbonic acid calcium;
In the sodium hydroxide solution reclaiming in step S4, add salt acid for adjusting pH to 5-6, after filtration, washing, after dry protein.
2. the preparation method of chitosan according to claim 1, is characterized in that, the mass concentration of hydrochloric acid described in step S3 is 10-15%, and described soak time is 10-15 hour.
3. the preparation method of chitosan according to claim 1, is characterized in that, the mass concentration of sodium hydroxide described in step S4 is 8-10%, and described boiling temps is 80-90 ℃, boils while stirring as 2-3 hour.
4. the preparation method of chitosan according to claim 1, it is characterized in that, the mass concentration of potassium permanganate described in step S5 is 1%, soak time is 1-2 hour, described reductive agent is one or more in Sulfothiorine, sodium bisulfite, oxalic acid, and the mass concentration of described reductive agent is 1-1.5%.
5. the preparation method of chitosan according to claim 1, is characterized in that, the mass concentration of sodium hydroxide described in step S6 is 40-50%.
6. prepare the liquid-immersion device of chitosan as claim 1-5 for one kind, it is characterized in that, this liquid-immersion device comprises that top has the outer cylinder body of opening (1) and inner barrel (2), it is characterized in that, described outer cylinder body (1) and inner barrel (2) are cylindric, the external diameter of described inner barrel (2) is less than the internal diameter of outer cylinder body (1), the height of inner barrel (2) is less than the height of outer cylinder body (1), described inner barrel (2) is connected on outer cylinder body (1) by a demountable structure, the bottom of described inner barrel (2) offers some liquid drain holes (3), on described outer cylinder body (1) outer side wall, be connected with input duct (19), described input duct (19) is connected for acid solution device with one, in input duct (19), be also provided with liquid inlet electromagnetic valve (5), described outer cylinder body (1) bottom is connected with fluid pipeline (20), on fluid pipeline (20), be provided with liquid outlet electromagnetic valve (7), on the inwall of described outer cylinder body (1) bottom, be fixed with pH value sensor (8), on the outer wall of described outer cylinder body (1), be fixed with controller (9), described pH value sensor (8), liquid outlet electromagnetic valve (7) is all connected with this controller (9) by circuit with liquid inlet electromagnetic valve (5).
7. prepare according to claim 6 the liquid-immersion device of chitosan, it is characterized in that, on described outer cylinder body (1) outer side wall, offer inlet opening (4), described input duct (19) is connected with described inlet opening (4), described outer cylinder body (1) bottom offers fluid hole (6), described fluid pipeline (20) is connected with described fluid hole (6), and described fluid pipeline (20) is connected with a collection box (18).
8. prepare according to claim 7 the liquid-immersion device of chitosan, it is characterized in that, described confession acid solution device comprises acid storing tank (10) and water pump (11), the inlet pipe of described water pump (11) is connected with acid storing tank (10), the pipe that goes out of described water pump (11) is connected with above-mentioned input duct (19), and water pump (11) is connected with described controller (9) by circuit.
9. according to the liquid-immersion device of preparing chitosan described in claim 6 or 7 or 8, it is characterized in that, described demountable structure comprises hook one (12) and hook two (13), described hook one (12) and hook two (13) are separately fixed at the corresponding place, top of inner barrel (2), and hook one (12) and hook two (13) hanging supports are at the place, top of outer cylinder body (1).
10. according to the liquid-immersion device of preparing chitosan described in claim 6 or 7 or 8, it is characterized in that, described demountable structure comprises steady brace one (14) and steady brace two (15), place, described outer cylinder body (1) top offers corresponding breach one (16) and breach two (17), one end of described steady brace one (14) is fixed on the outer wall on inner barrel (2) top, the other end of steady brace one (14) is placed in described breach one (16), one end of described steady brace two (15) is fixed on the outer wall on inner barrel (2) top, the other end of steady brace two (15) is placed in described breach two (17).
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