CN1548461A - Production process and apparatus of high quality chitosan - Google Patents
Production process and apparatus of high quality chitosan Download PDFInfo
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- CN1548461A CN1548461A CNA031168221A CN03116822A CN1548461A CN 1548461 A CN1548461 A CN 1548461A CN A031168221 A CNA031168221 A CN A031168221A CN 03116822 A CN03116822 A CN 03116822A CN 1548461 A CN1548461 A CN 1548461A
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Abstract
The present invention relates to relates to chitosan producing technology. The production process o chitosan includes the following steps: soaking crushed chitin in sodium hydroxide solution of 40-55 wt% concentration for 12-36 hr; microwave and alkali treatment comprising the microwave heating of the soaked mixture at 110-160 deg.c for 0.5-1.5 hr, water washing to neutrality, re-adding sodium hydroxide solution of 40-55 wt% concentration, microwave heating of the soaked mixture at 110-160 deg.c for another 0.5-1.5 hr and water washing to neutrality again; and drying to obtain the chitosan product. The microwave apparatus is also provided. The present invention has short heating time, high chitosan product quality and other advantages, and is suitable for industrial application.
Description
Technical field
The present invention relates to a kind of chitosan production method technical field, especially relate to the technical field that microwave method is produced chitosan, the invention still further relates to its production equipment technical field.
Background technology
Crust usually claims chitin, mainly is present in the shell of arthropods such as shrimp crab, the body surface of insect, and in the cell walls of fungi.And chitosan is chitin deacetylase based products (typically referring to the deacetylation more than 60%).Chitosan and derivative thereof are widely applied to fields such as agricultural, food, medicine, daily use chemicals, weaving, printing and dyeing, metal recovery and environmental protection.Along with people use and going deep into of studying it, particularly find the oligosaccharide of 3-9 chitosan sugar, have obviously pharmacological actions such as the tumor growth of inhibition, blood fat reducing and cholesterol, increase body immune function, will guarantee to be used for intravenous wholesomeness when still using.The enzymolysis or the acidolysis of normal chitosan not only exist molecular weight distribution wide, but also have a large amount of impurity (comprise enzymolysis after nubbin).The existence of these impurity even under micro-situation, also may cause the toxicity that should not occur.Therefore, highly purified chitosan is the important prerequisite of the technological development of preparation intravenously administrable agent.Cosmetics also need highly purified chitosan as its raw material in addition.Though also prepare the technology report of high purity of shell glycan production method relevant for microwave method; it as the patent No. 98110327.8 Chinese patent " novel method of deacetylation of chitin "; this method is characterized in that this method comprising the following steps: (1) to get the chitin work in-process, and to put into concentration be that 40～55% sodium hydroxide solution soaks; (2) immersion treated that being put into microwave oven together with the container that soaks usefulness after chitin is soaked into all heated 1～4.5 hour in 0.5～3 hour; (3) immediately the above-mentioned half-finished container of immersion chitin is taken out from microwave oven after heating stops and pour heated soak in it in the squeezing machine remaining soak solution of squeezing removal; (4) treat that putting into clear water after above-mentioned press for extracting juice goes the material of soak solution to naturally cool to 45 °～55 ℃ washs; till checking nondiscoloration with phenolphthalein indicator; (5) oven dry is crushed to required order number; embodiment shows the product that can obtain deacetylation about 87% in this patent application; so quality is also not high; still be difficult on fields such as medicines and health protection, well be used; this microwave heating needs 1～4.5 hour in addition; time is long partially; production efficiency is lower; inconvenient operation proposes higher requirement to production equipment simultaneously.Though in actual production, also used the microwave heating installation of tunnel like design, but reveal in order to prevent microwave, the height of importing and exporting has only 60 centimetres, so work capacity is very little, also need to be with gloves to take out container, carry out deacetylation again after to be cooled clean, operate very inconveniently, do not meet the suitability for industrialized production requirement.
Summary of the invention
Primary technical problem to be solved by this invention be provide at prior art that a kind of microwave heating number of times is few, heat-up time short, easy to operate and obtain the high-quality chitosan production method of chitosan deacetylation rate height, quality quality better.
Another technical problem to be solved by this invention provide a kind of use aforesaid method, reasonable in design simple, implement easily, easy to operate, isolated plant that production efficiency is high.
The present invention solves the technical scheme that above-mentioned primary technical problem adopts: a kind of chitosan production method, it is characterized in that steps in sequence is: (1) alkali soaks step, to put in the container after the chitin pulverizing, the sodium hydroxide solution that adds mass concentration 40-55% then soaks, soak time is 12-36 hour, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: the 10-30 milliliter; (2) microwave alkali treatment, said mixture is placed in the microwave device, under 110-160 ℃ of condition, carried out reacting by heating 0.5-1.5 hour, be washed to neutrality then, the sodium hydroxide solution that adds mass concentration 40-55% again, quality of material and sodium hydroxide solution volume ratio remain 1 gram: 10-30 milliliter, mixture still are placed in the microwave device, under 110-160 ℃ of condition, carry out reacting by heating 0.5-1.5 hour, and then be washed to neutrality; (3) drying step carries out drying with material, has obtained the chitosan product.
As the optimisation technique scheme, it is 45% that above-mentioned alkali soaks its sodium hydroxide solution of step, and soak time is 24 hours, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 25 milliliters; Above-mentioned its sodium hydroxide solution of microwave alkali treatment is 45%, reacting by heating 1 hour, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 25 milliliters; The tap water of deionized water or process purifying treatment is selected in above-mentioned washing for use; The interrupter method washing is adopted in above-mentioned washing, and time interval controls was at 8-12 minute, and control its specific conductivity in washing back is in 0-90 μ S/cm scope.
Its production stage of above-mentioned chitin is followed successively by: raw material soaks through the 3-7% sodium hydroxide solution, and the clear water washing is to neutral; Pass through 4-6% hydrochloric acid acidleach for the first time 12-36 hour again, the clear water washing is to neutral; Pass through 8-12% sodium hydroxide solution soda boiling 0.5-1.5 hour then, the clear water washing is to neutral; Pass through 8-10% hydrochloric acid acidleach for the second time 3-5 hour again, be washed to neutrality, deionized water soaked 3-6 hour, again washing; Daylight shines white, obtains chitin.
The present invention solves the technical scheme that another technical problem adopts: its isolated plant is that wave device structure is to be mounted with the tetrafluoroethylene tube in the anchor of device, the tube bottom drain hole is connected with valve, top port is by the retaining plate fixed motor, agitator is installed on the motor output shaft, retaining plate has charging opening in the side simultaneously, be lagging material between tetrafluoroethylene tube and the anchor, a plurality of microwave generators are fixed on the anchor, and its emitting surface is at the tetrafluoroethylene tube.
Above-mentioned microwave generator is equally distributed facing to the stack shell surface of tetrafluoroethylene tube.
Above-mentioned valve top is provided with the temperature-sensitive head of temperature measuring equipment, measures temperature of charge.
Compared with prior art; the invention has the advantages that: it is few that this production method has a microwave heating number of times; general requirement 2 times is just passable; microwave heating time is short; in general 1.5 hours; and the bonding gap washing, can obtain the chitosan of 97.12% deacetylation, in the embodiment of optimizing; can obtain the chitosan of 98.8% deacetylation; so can obtain the chitosan of high deacetylation in the basic identical time, and ash content is smaller or equal to 0.2%, moisture is smaller or equal to 10%; arsenic content is smaller or equal to 0.5 mg/kg; mercury content is smaller or equal to 0.3 mg/kg, and lead content is smaller or equal to 1 mg/kg, and the bacterium number is less than 10
3Individual/gram, pathogenic bacterium must not detect, so be a kind of high-quality chitosan, can well be used in a lot of fields such as fields such as medicines and health protection, makeup, and be used the special microwave device of this method, can be enhanced productivity greatly, be fit to the high-quality chitosan of suitability for industrialized production, and it is simple and practical, easy to manufacture and use, easy to operate.
Description of drawings
The wave device structure amplification view that Fig. 1 the inventive method is adopted.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
The production of A chitin selects for use cicada shell or lobster shell to do raw material, generally pulverize in 2 centimetres squares, soak through 5% sodium hydroxide solution earlier, the clear water washing is to neutral, through 5% hydrochloric acid acidleach for the first time 24 hours, note keeping as far as possible low temperature again, the clear water washing is to neutral then, again through 10% sodium hydroxide solution soda boiling 1 hour, to neutral, through 9% hydrochloric acid acidleach for the second time 4 hours, be washed to neutrality with the clear water washing then, deionized water soaked 4 hours, washing again, daylight shines white, obtains chitin, water can adopt the tap water through purifying treatment, adopts deionized water better certainly.The chitin quality that this method obtains is good, productive rate is high, cost is low, and the chitosan ash control that can make finished product reduces waste liquid amount, compliance with environmental protection requirements 0.2%.
The B chitosan is produced
(1) alkali soaks the container of putting into device after step is pulverized chitin, and the sodium hydroxide solution that adds mass concentration 45% then soaks, and soak time is 24 hours, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 25 milliliters;
(2) the microwave alkali treatment is placed into said mixture in the microwave device, under 130 ℃ of conditions, carried out reacting by heating 1 hour, be washed to neutrality then, the sodium hydroxide solution that adds mass concentration 45% again, quality of material and sodium hydroxide solution volume ratio remain 1 gram: 25 milliliters, mixture still is placed in the microwave device, carries out reacting by heating 1 hour under 130 ℃ of conditions, and then being washed to neutrality, control its specific conductivity in washing back is in 0-90 μ S/cm scope; Select the tap water of deionized water or process purifying treatment in the washing for use; and the interrupter method washing is adopted in washing, is exactly the certain hour washing more at interval at interval of washing back, and time interval controls was at 10 minutes; help like this sodium-acetate that echos on the material surface is removed, improve the deacetylation rate.
(3) drying step carries out drying with material; obtained the chitosan product; its deacetylation rate reaches more than 98.8%; and ash content is smaller or equal to 0.2%; moisture is smaller or equal to 10%, and arsenic content is smaller or equal to 0.5 mg/kg, and mercury content is smaller or equal to 0.3 mg/kg; lead content is smaller or equal to 1 mg/kg, and the bacterium number is less than 10
3Individual/gram, pathogenic bacterium must not detect, and are a kind of high-quality chitosans, can well be used in a lot of fields such as fields such as medicines and health protection, makeup.
In the above-mentioned production; microwave heating power can be decided with material; we carried out 500 watts/10 gram chitin experiments in lab scale; greatly to 8000 watts/5 kilograms chitinous pilot scales; can realize; finally obtained the product of deacetylation rate more than 98%, and be incubated 1-2 hour after the microwave heating, effect is better.
The wave device structure that present embodiment adopts as schematically shown in Figure 1, be mounted with tetrafluoroethylene tube 6 in the anchor 9 of device, tube bottom drain hole 8 is connected with valve, the valve top is provided with the temperature-sensitive head of temperature measuring equipment, measure temperature of charge, port is by retaining plate 2 fixed motors 4 above the tetrafluoroethylene tube 6, agitator 5 is installed on the motor output shaft, retaining plate 2 has charging opening 3 in the side simultaneously, be lagging material 7 between tetrafluoroethylene tube 6 and the anchor 9, a plurality of microwave generators 1 are fixed on the anchor 9, its emitting surface is at tetrafluoroethylene tube 6, and general microwave generator 1 can be evenly distributed in tetrafluoroethylene tube 6 stack shell periphery.Being equipped with the storage of moving below tetrafluoroethylene tube bottom drain hole irritates.When it uses, to soak chitin that step process crosses through alkali is put in the tetrafluoroethylene tube in the microwave device by charging opening, again the sodium hydroxide solution of alkali lye preparing tank is put into by charging opening with pump in the tetrafluoroethylene tube of microwave device and goes, starting electric motor then stirs, and heat and react with microwave generator, after reaction times arrives, emit by drain hole again, be put in the mobile storage filling, pump lixiviating liquid anhydrates and washes, and then the material collection after will washing gets up to be put in the tetrafluoroethylene tube of microwave device, add alkali lye, microwave heating treatment once is put into mixture in the mobile storage filling pump lixiviating liquid more according to the method described above, anhydrate and wash, control its specific conductivity in washing back is in 0-90 μ S/cm scope, and is dry then, obtains final product chitosan.
Embodiment 2:
The production of A chitin has adopted snow crab shell or mantis shrimp shell to do raw material, and other obtains the fine chitin as the method for embodiment.
The B chitosan is produced
(1) alkali soaks the container of putting into device after step is pulverized chitin, and the sodium hydroxide solution that adds mass concentration 55% then soaks, and soak time is 12 hours, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 10 milliliters;
(2) the microwave alkali treatment is placed into said mixture in the microwave device, under 110 ℃ of conditions, carried out reacting by heating 0.5 hour, be washed to neutrality then, the sodium hydroxide solution that adds mass concentration 55% again, quality of material and sodium hydroxide solution volume ratio remain 1 gram: 10 milliliters, mixture still is placed in the microwave device, carries out reacting by heating 0.5 hour under 110 ℃ of conditions, and then being washed to neutrality, control its specific conductivity in washing back is in 0-90 μ S/cm scope; Select the tap water of deionized water or process purifying treatment in the washing for use; and the interrupter method washing is adopted in washing, is exactly the certain hour washing more at interval at interval of washing back, and time interval controls was at 12 minutes; help like this sodium-acetate that echos on the material surface is removed, improve the deacetylation rate.
(3) drying step carries out drying with material; obtained the chitosan product; its deacetylation rate reaches more than 97.2%; and ash content is smaller or equal to 0.2%; moisture is smaller or equal to 10%, and arsenic content is smaller or equal to 0.5 mg/kg, and mercury content is smaller or equal to 0.3 mg/kg; lead content is smaller or equal to 1 mg/kg, and the bacterium number is less than 10
3Individual/gram, pathogenic bacterium must not detect, and are a kind of high-quality chitosans, can well be used in a lot of fields such as fields such as medicines and health protection, makeup.
Embodiment 3:
The production of A chitin has adopted snow crab shell or mantis shrimp shell to do raw material, and other obtains the fine chitin as the method for embodiment.
The B chitosan is produced
(1) alkali soaks the container of putting into device after step is pulverized chitin, and the sodium hydroxide solution that adds mass concentration 40% then soaks, and soak time is 36 hours, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 30 milliliters;
(2) the microwave alkali treatment is placed into said mixture in the microwave device, under 160 ℃ of conditions, carried out reacting by heating 1.5 hours, be washed to neutrality then, the sodium hydroxide solution that adds mass concentration 40% again, quality of material and sodium hydroxide solution volume ratio remain 1 gram: 30 milliliters, mixture still is placed in the microwave device, carries out reacting by heating 1.5 hours under 160 ℃ of conditions, and then being washed to neutrality, control its specific conductivity in washing back is in 0-90 μ S/cm scope; Select the tap water of deionized water or process purifying treatment in the washing for use; and the interrupter method washing is adopted in washing, is exactly the certain hour washing more at interval at interval of washing back, and time interval controls was at 8 minutes; help like this sodium-acetate that echos on the material surface is removed, improve the deacetylation rate.
(3) drying step carries out drying with material; obtained the chitosan product; its deacetylation rate reaches more than 98.4%; and ash content is smaller or equal to 0.2%; moisture is smaller or equal to 10%, and arsenic content is smaller or equal to 0.5 mg/kg, and mercury content is smaller or equal to 0.3 mg/kg; lead content is smaller or equal to 1 mg/kg, and the bacterium number is less than 10
3Individual/gram, pathogenic bacterium must not detect, and are a kind of high-quality chitosans, can well be used in a lot of fields such as fields such as medicines and health protection, makeup.
Embodiment 4:
The production of A chitin has adopted cicada shell or mantis shrimp shell to do raw material, and other obtains the fine chitin as the method for embodiment.
The B chitosan is produced
(1) alkali soaks the container of putting into device after step is pulverized chitin, and the sodium hydroxide solution that adds mass concentration 48% then soaks, and soak time is 24 hours, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 15 milliliters;
(2) the microwave alkali treatment is placed into said mixture in the microwave device, under 140 ℃ of conditions, carried out reacting by heating 1 hour, be washed to neutrality then, the sodium hydroxide solution that adds mass concentration 48% again, quality of material and sodium hydroxide solution volume ratio remain 1 gram: 15 milliliters, mixture still is placed in the microwave device, carries out reacting by heating 1 hour under 140 ℃ of conditions, and then being washed to neutrality, control its specific conductivity in washing back is in 0-90 μ S/cm scope; Select the tap water of deionized water or process purifying treatment in the washing for use; and the interrupter method washing is adopted in washing, is exactly the certain hour washing more at interval at interval of washing back, and time interval controls was at 10 minutes; help like this sodium-acetate that echos on the material surface is removed, improve the deacetylation rate.
(3) drying step carries out drying with material; obtained the chitosan product; its deacetylation rate reaches more than 97.6%; and ash content is smaller or equal to 0.2%; moisture is smaller or equal to 10%, and arsenic content is smaller or equal to 0.5 mg/kg, and mercury content is smaller or equal to 0.3 mg/kg; lead content is smaller or equal to 1 mg/kg, and the bacterium number is less than 10
3Individual/gram, pathogenic bacterium must not detect, and are a kind of high-quality chitosans, can well be used in a lot of fields such as fields such as medicines and health protection, makeup.
Claims (10)
1, a kind of high-quality chitosan production method is characterized in that steps in sequence is:
(1) alkali soaks step, puts in the container after chitin is pulverized, and the sodium hydroxide solution that adds mass concentration 40-55% then soaks, and soak time is 12-36 hour, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: the 10-30 milliliter;
(2) microwave alkali treatment, said mixture is placed in the microwave device, under 110-160 ℃ of condition, carried out reacting by heating 0.5-1.5 hour, be washed to neutrality then, the sodium hydroxide solution that adds mass concentration 40-55% again, quality of material and sodium hydroxide solution volume ratio remain 1 gram: 10-30 milliliter, mixture still are placed in the microwave device, under 110-160 ℃ of condition, carry out reacting by heating 0.5-1.5 hour, and then be washed to neutrality;
(3) drying step carries out drying with material, has obtained the chitosan product.
2, production method according to claim 1 is characterized in that it is 45% that described alkali soaks its sodium hydroxide solution of step, and soak time is 24 hours, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 25 milliliters.
3, production method according to claim 1 is characterized in that described its sodium hydroxide solution of microwave alkali treatment is 45%, reacting by heating 1 hour, and chitin quality and sodium hydroxide solution volume ratio are 1 gram: 25 milliliters.
4,, it is characterized in that deionized water is selected in described washing for use or through the tap water of purifying treatment according to claim 1 or 2 or 3 described production methods.
5, according to claim 1 or 2 or 3 described production methods, it is characterized in that the washing of described washing employing interrupter method, time interval controls was at 8-12 minute, and control its specific conductivity in washing back is in 0-90 μ S/cm scope.
6, production method according to claim 1 is characterized in that its production stage of described chitin is followed successively by: raw material soaks through the 3-7% sodium hydroxide solution, and the clear water washing is to neutral; Pass through 4-6% hydrochloric acid acidleach for the first time 12-36 hour again, the clear water washing is to neutral; Pass through 8-12% sodium hydroxide solution soda boiling 0.5-1.5 hour then, the clear water washing is to neutral; Pass through 8-10% hydrochloric acid acidleach for the second time 3-5 hour again, be washed to neutrality, deionized water soaked 3-6 hour, again washing; Daylight shines white, obtains chitin.
7, production method according to claim 6 is characterized in that described raw material selects snow crab shell, cicada shell, mantis shrimp shell or lobster shell for use.
8, a kind of isolated plant that in method according to claim 1, uses, it is characterized in that its structure of microwave device is to be mounted with tetrafluoroethylene tube (6) in the anchor (9) of device, tube bottom drain hole (8) is connected with valve, top port is fixed with electric motor (4) by retaining plate (2), agitator (5) is installed on the motor output shaft, retaining plate has charging opening (3) in the side simultaneously, be lagging material (7) between tetrafluoroethylene tube (6) and the anchor (9), a plurality of microwave generators (1) are fixed on the anchor (9), and its emitting surface is at tetrafluoroethylene tube (6).
9, production method according to claim 8 is characterized in that described microwave generator (1) is equally distributed facing to the stack shell surface of tetrafluoroethylene tube (6).
10, production method according to claim 9 is characterized in that described tetrafluoroethylene tube (6) bottom is provided with temperature measuring equipment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031168221A CN1300177C (en) | 2003-05-07 | 2003-05-07 | Production process and apparatus of high quality chitosan |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031168221A CN1300177C (en) | 2003-05-07 | 2003-05-07 | Production process and apparatus of high quality chitosan |
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| CN1548461A true CN1548461A (en) | 2004-11-24 |
| CN1300177C CN1300177C (en) | 2007-02-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200505B (en) * | 2007-11-29 | 2011-01-19 | 湖北东方天琪生物工程股份有限公司 | Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell |
| CN105218698A (en) * | 2014-06-06 | 2016-01-06 | 连云港碳谷材料科技有限公司 | A kind of take shrimp and crab shells as the method that raw material prepares hydroxyapatite and chitosan |
| CN107118287A (en) * | 2017-06-04 | 2017-09-01 | 陈泽勇 | A kind of high purity of shell glycan production method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1210867A (en) * | 1998-07-02 | 1999-03-17 | 许光庭 | New deacetylation of chitin |
| CN1281631C (en) * | 2002-02-07 | 2006-10-25 | 徐云龙 | Microwave process for preparing carboxymethyl chitosan |
-
2003
- 2003-05-07 CN CNB031168221A patent/CN1300177C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200505B (en) * | 2007-11-29 | 2011-01-19 | 湖北东方天琪生物工程股份有限公司 | Method for preparing high deacetylate degree and high viscosity chitosan by using shrimp shell |
| CN105218698A (en) * | 2014-06-06 | 2016-01-06 | 连云港碳谷材料科技有限公司 | A kind of take shrimp and crab shells as the method that raw material prepares hydroxyapatite and chitosan |
| CN105218698B (en) * | 2014-06-06 | 2017-07-07 | 浙江海富海洋生物科技有限公司 | A kind of method for preparing hydroxyapatite and shitosan as raw material with shrimp and crab shells |
| CN107118287A (en) * | 2017-06-04 | 2017-09-01 | 陈泽勇 | A kind of high purity of shell glycan production method |
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| Publication number | Publication date |
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| CN1300177C (en) | 2007-02-14 |
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