CN105770941B - The sterilizing methods of chitosan and chitosan derivatives - Google Patents
The sterilizing methods of chitosan and chitosan derivatives Download PDFInfo
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- CN105770941B CN105770941B CN201410794583.XA CN201410794583A CN105770941B CN 105770941 B CN105770941 B CN 105770941B CN 201410794583 A CN201410794583 A CN 201410794583A CN 105770941 B CN105770941 B CN 105770941B
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Abstract
The present invention relates to a kind of chitosan and the sterilizing methods of chitosan derivatives, including:According to mass ratio it is 1 by water and ethanol:0.05 to 1:20 are mixed to get water-ethanol mixed liquor;The water-ethanol mixed liquor is stirred evenly by being added in chitosan or chitosan derivatives, fills high temperature resistant bag;The high temperature resistant bag is placed at temperature as 101 DEG C~108 DEG C, pressure is under 1.10MPa~1.15MPa, and pressure-maintaining and heat-preservation sterilizes 30 minutes~60 minutes;Treat that temperature is down to less than 50 DEG C, take out the high temperature resistant bag.The sterilizing methods of chitosan and chitosan derivatives of the present invention are combined by adding water-ethanol mixed liquor with high temperature and pressure moist heat sterilization, substantially increase the efficiency of sterilizing.Due to adding water-ethanol mixed liquor, the penetration power and efficiency of high steam are improved, heat transfer rate is accelerated, and the bacterium inside product particle also can be quickly killed.
Description
Technical field
The present invention relates to a kind of sterilizing methods, more particularly to the sterilizing methods of a kind of chitosan and chitosan derivatives.
Background technology
Chitosan also known as chitin, chitosan, chitosan, Chitosan, chitosamine, chitosan, crust
Polysaccharide, glycosaminoglycan etc., English name Chitosan, molecular structural formula are:
Chemical name:Polydextrose An ﹙ 1-4) -2- amino-beta-D glucose
Chitosan is chitin obtained product after deacetylation, and chitosan, which has, improves immune, activating cell, pre-
The effects such as anti-cancer, reducing blood lipid, blood pressure lowering, anti-aging, adjusting body environment, available for medicine, health care, field of food.Shell gathers
Sugar can be used for sewage disposal, protein salvage, Water warfare etc..Field of functional materials, chitosan can be used for membrane material, carrier, absorption
Agent, fiber, medical material etc..In light textile field, chitosan can be used for textile finishing, health care underwear, paper making additive etc..In agricultural
Field, available for feed addition, seed treatment, soil improvement, fruit freshness preserving etc..In Field of Tobacco, chitosan is functional
Reconstituted tobacoo glue, and with improve mouthfeel, burn free from extraneous odour the features such as.
Chitosan is mainly extracted from shrimp shell, crab shell, housefly, silkworm chrysalis and microorganism etc. at present, and technique is usually through acid
Decalcification, alkali degreasing and protein and be processed into chitin, then add alkali deacetylate to form chitosan by chitin.Due to whole
Cleaned in a production process with substantial amounts of water, and chitosan is a kind of linear polysaccharide in itself, this is just various microorganisms and thin
The suitable growing environment that bacterium creates, after testing, the high density chitosan total number of bacteria by sterilizing up to 2 ×
105CFU/g, so high bacterial number are not used to field of food, can not be used for field of medicaments, so before use
It must pass through sterilization treatment.Common high temperature and pressure moist heat sterilization is sterilized 15 minutes at 121 DEG C, this is for as chitosan
Linear polysaccharide is unfavorable, because chitosan can largely be decomposed and aoxidized at this high temperature, color is also by off-white color
It is changed into bronzing, product has been denatured, and can not be used.And sterilising temp is reduced, bacterium cannot thoroughly be killed again.
The content of the invention
A kind of the defects of the purpose of the present invention is for the prior art, there is provided sterilizing side of chitosan and chitosan derivatives
Method, can both ensure that product in the case where not destroying the chitosan to be sterilized and chitosan derivatives molecular structure
Safety in utilization can effectively kill bacterium at the same time.
To achieve the above object, the present invention provides a kind of chitosan and the sterilizing methods of chitosan derivatives, the side
Method comprises the following steps:
Step 1, it is 1 according to mass ratio by water and ethanol:0.05 to 1:20 are mixed to get water-ethanol mixed liquor;
Step 2, the water-ethanol mixed liquor is stirred evenly by being added in chitosan or chitosan derivatives, filled resistance to
Temperature bag;The percentage that the water-ethanol mixed liquor accounts for total material is 20%~50% (w/w);
Step 3, the high temperature resistant bag is placed at temperature as 101 DEG C~108 DEG C, pressure is 1.10MPa~1.15MPa
Under, pressure-maintaining and heat-preservation sterilizes 30 minutes~60 minutes;
Step 4, treat that temperature is down to less than 50 DEG C, take out the high temperature resistant bag.
Further, further included before the step 1:Low-density chitosan, bulk density are made by shellfish
For 0.2g/ml~0.4g/ml;High density chitosan is made in low-density chitosan processing, bulk density is more than 0.4g/
ml。
Further, further included before the step 1:It is prepared by chitosan molecule structure is modified or is modified
Compound.
Further, the mass ratio of water and ethanol is 1 in the step 1:0.1 to 1:0.4.
Further, in the step 2 water-ethanol of chitosan or chitosan derivatives mixing liquid hold-up quality hundred
Divide than being 21%~27%.
Further, car is placed in high pressure specifically, the high temperature resistant bag is placed on charge car pallet by the step 3
In the Sterilization Kettle of sterilizing installation, 101 DEG C~108 DEG C of temperature is controlled, control pressure is gone out in 1.10MPa~1.15MPa, pressure-maintaining and heat-preservation
Bacterium 30 minutes~60 minutes.
Further, temperature is 101 DEG C~105 DEG C in the step 3, and pressure is 1.11MPa~1.14MPa.
Further, sterilization time is 45 minutes~60 minutes in the step 3.
Further, the step 4 is specifically, close the steam valve of autoclaving equipment, slowly pressure release, treats the height
Pressure sterilizing installation is cooled to less than 50 DEG C, takes out the high temperature resistant bag.
Further, the temperature is down to 40 DEG C.
The sterilizing methods of chitosan and chitosan derivatives of the present invention are wet with high temperature and pressure by adding water-ethanol mixed liquor
Heat sterilization is combined, and substantially increases the efficiency of sterilizing.Due to adding water-ethanol mixed liquor, wearing for high steam is improved
Saturating power and efficiency, heat transfer rate are accelerated, and the bacterium inside product particle also can be quickly killed.
Brief description of the drawings
Fig. 1 is the flow chart of the sterilizing methods of chitosan of the present invention and chitosan derivatives.
Embodiment
Below by drawings and examples, technical scheme is described in further detail.
Fig. 1 is the flow chart of the sterilizing methods of chitosan of the present invention and chitosan derivatives, as shown in the figure, the present invention is specific
Include the following steps:
Step 101, it is 1 according to mass ratio by water and ethanol:0.1 to 1:0.4 is mixed to get water-ethanol mixed liquor;
In addition, the process for preparing chitosan and chitosan derivatives can also be included before step 101, it is specially:
It is to be made low-density chitosan by shellfish such as shrimp, crabs to prepare chitosan, bulk density for 0.2g/ml~
0.4g/ml;Low-density chitosan is handled and high density chitosan is made, bulk density is more than 0.4g/ml.
And prepare prepared by chitosan derivatives refer to that chitosan molecule structure is modified or is modified variousization
Compound, as chitosan hydrochloride, chitosan acetate, chitosan lactate, chitosan quaternary ammonium salt, chitosan phosphate, shell gather
Sugared citrate, O-carboxymethyl chitosan, N, O-carboxymethyl chitosan, sulfated chitosan, N-trimethyl chitin, N-
Nmaleoyl chitosan, hydroxypropyl chitosan, Alendronate sodium chitosan, β-cyclodextrin meet skill chitosan, N, O-ethoxy
Chitosan etc..
Preferably, the mass ratio of water and ethanol is 1 in step 101:0.1 to 1:0.4.
Step 102, water-ethanol mixed liquor is stirred evenly by being added in chitosan or chitosan derivatives, fills resistance to height
Warm bag;
Preferably, the percentage that the water-ethanol mixed liquor of chitosan or chitosan derivatives accounts for total material is 20%
~50% (w/w).
Step 103, high temperature resistant bag being placed at temperature as 101 DEG C~108 DEG C, pressure is under 1.10MPa~1.15MPa,
Pressure-maintaining and heat-preservation sterilizes 30~60 minutes;
Specifically, high temperature resistant bag is placed on charge car pallet, car is placed in the Sterilization Kettle of autoclaving equipment, is controlled
101 DEG C~108 DEG C of temperature, control pressure sterilize 30 minutes~60 minutes in 1.10MPa~1.15MPa, pressure-maintaining and heat-preservation.
Preferably, temperature is 101 DEG C~105 DEG C, and pressure is 1.11MPa~1.14MPa.Sterilization time is 45 minutes~60
Minute.
Step 104, treat that temperature is down to less than 50 DEG C, take out high temperature resistant bag.
Specifically, close autoclaving equipment steam valve, slowly pressure release, treat autoclaving equipment be cooled to 50 DEG C with
Under, take out high temperature resistant bag.
Preferably, temperature is down to 40 DEG C.
Embodiment 1
Step 201,1 kilogram of water and 0.1 kilogram of ethanol is weighed respectively, and water is uniformly mixed with ethanol, obtains water-ethanol
Mixed liquor;
Step 202,4 kilograms of chitosan (low-density) is weighed slowly to pour into charge groove, then by water-ethanol mixed liquor
In charge groove, stir evenly, obtain aqueous-alcohol mixeding liquid (1:0.1) 21.57% chitosan (low-density) wet feed, then
This wet feed is loaded in high temperature resistant cloth bag again, ties sack;
Step 203, the high temperature resistant cloth bag equipped with chitosan (low-density) is placed on charge car pallet, car is pushed into high pressure
In the Sterilization Kettle of sterilizing installation, 102 DEG C~104 DEG C of temperature is controlled, control pressure is gone out in 1.11MPa~1.14MPa, pressure-maintaining and heat-preservation
Bacterium 45 minutes;
Step 204, after the completion of sterilizing, steam off valve, slowly pressure release, treat autoclaving equipment be cooled to 40 DEG C with
Under, the high temperature resistant bag is taken out, chitosan (low-density) is taken out from bag, carries out total number of bacteria, mould and yeast sum
Detection.
The microbiological data in chitosan (low-density) by above-mentioned sterilization treatment (wherein also list as shown in table 1
The data of microorganism contained by the chitosan (low-density) of non-sterilized processing).
Table 1
Embodiment 2
Step 301,1 kilogram of water and 0.3 kilogram of ethanol is weighed respectively, and water is uniformly mixed with ethanol, obtains water-ethanol
Mixed liquor;
Step 302,4.5 kilograms of chitosan (high density) is weighed slowly to fall in charge groove, then by water-ethanol mixed liquor
Enter in charge groove, stir evenly, obtain aqueous-alcohol mixeding liquid (1:0.4) 22.41% chitosan (high density) wet feed, so
This wet feed is loaded in high temperature resistant cloth bag again afterwards, ties sack;
Step 303, the high temperature resistant cloth bag equipped with chitosan (high density) is placed on charge car pallet, car is pushed into high pressure
In the Sterilization Kettle of sterilizing installation, 102 DEG C~104 DEG C of temperature is controlled, control pressure is gone out in 1.11MPa~1.14MPa, pressure-maintaining and heat-preservation
Bacterium 60 minutes;
Step 304, after the completion of sterilizing, steam off valve, slowly pressure release, treat autoclaving equipment be cooled to 40 DEG C with
Under, the high temperature resistant bag is taken out, chitosan (high density) is taken out from bag, carries out total number of bacteria, mould and yeast sum
Detection.
The microbiological data in chitosan (high density) by above-mentioned sterilization treatment (wherein also list as shown in table 2
The data of microorganism contained by the chitosan (high density) of non-sterilized processing).
Table 2
Embodiment 3
Step 401,1 kilogram of water and 0.3 kilogram of ethanol is weighed respectively, and water is uniformly mixed with ethanol, obtains water-ethanol
Mixed liquor;
Step 402,4.5 kilograms of chitosan hydrochloride is weighed slowly to pour into charge groove, then by water-ethanol mixed liquor
In charge groove, stir evenly, obtain aqueous-alcohol mixeding liquid (1:0.3) 22.41% chitosan hydrochloride wet feed, Ran Houzai
This wet feed is loaded in high temperature resistant cloth bag, ties sack;
Step 403, the high temperature resistant cloth bag equipped with chitosan hydrochloride is placed on charge car pallet, car push-in high pressure is gone out
In the Sterilization Kettle of bacterium equipment, 102 DEG C~104 DEG C of temperature is controlled, control pressure is in 1.11MPa~1.14MPa, pressure-maintaining and heat-preservation sterilizing
45 minutes;
Step 404, after the completion of sterilizing, steam off valve, slowly pressure release, treat autoclaving equipment be cooled to 40 DEG C with
Under, the high temperature resistant bag is taken out, chitosan hydrochloride is taken out from bag, carries out the inspection of total number of bacteria, mould and yeast sum
Survey.
The microbiological data in chitosan hydrochloride by above-mentioned sterilization treatment (wherein also list not as shown in table 3
The data of microorganism contained by the chitosan hydrochloride of sterilized processing).
Table 3
Embodiment 4
Step 501,1 kilogram of water and 0.4 kilogram of ethanol is weighed respectively, and water is uniformly mixed with ethanol, obtains water-ethanol
Mixed liquor;
Step 502,4.8 kilograms of O-carboxymethyl chitosan is weighed in charge groove, then by water-ethanol mixed liquor slowly
Pour into charge groove, stir evenly, obtain aqueous-alcohol mixeding liquid (1:0.4) 22.58% O-carboxymethyl chitosan wet feed,
Then this wet feed is loaded in high temperature resistant cloth bag again, ties sack;
Step 503, the high temperature resistant cloth bag equipped with O-carboxymethyl chitosan is placed on charge car pallet, car is pushed into high
In the Sterilization Kettle for pressing sterilizing installation, 102 DEG C~104 DEG C of temperature is controlled, control pressure is in 1.11MPa~1.14MPa, pressure-maintaining and heat-preservation
Sterilizing 50 minutes;
Step 504, after the completion of sterilizing, steam off valve, slowly pressure release, treat autoclaving equipment be cooled to 40 DEG C with
Under, the high temperature resistant bag is taken out, O-carboxymethyl chitosan is taken out from bag, carries out total number of bacteria, mould and yeast sum
Detection.
(wherein it also list as shown in table 4 by the microbiological data in O-carboxymethyl chitosan of above-mentioned sterilization treatment
The data of microorganism contained by O-carboxymethyl chitosan of non-sterilized processing).
Table 4
The chitosan of the present invention and the sterilizing methods of chitosan derivatives, in order not to be denatured product, add water-ethanol and mix
Liquid is closed, temperature is reduced, improves the penetration power and efficiency of high steam, protect not oxidized point of chitosan to greatest extent
Solution, and bacterium can be made thoroughly to be killed.The mechanism of this sterilizing methods is that ethanol can be denatured bacterioprotein, and high pressure is damp and hot
Sterilizing can deform the protein and nucleic acid of bacterium causes it dead.Water-ethanol mixed liquor, which adds, not only accelerates heat transfer, and
And the mixed vapour full of water and ethanol, oxygen tail off in Sterilization Kettle, avoid chitosan or chitosan derivatives by a large amount of oxygen
Change discoloration, and protect chitosan to greatest extent.
Above-described embodiment, has carried out the purpose of the present invention, technical solution and beneficial effect further
Describe in detail, it should be understood that the foregoing is merely the embodiment of the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution, improvement and etc. done, should all include
Within protection scope of the present invention.
Claims (10)
1. the sterilizing methods of a kind of chitosan and chitosan derivatives, it is characterised in that the described method comprises the following steps:
Step 1, it is 1 according to mass ratio by water and ethanol:0.05 to 1:20 are mixed to get water-ethanol mixed liquor;
Step 2, the water-ethanol mixed liquor is added in chitosan or chitosan derivatives and stirred evenly, fill high temperature resistant
Bag;The percentage that the water-ethanol mixed liquor accounts for total material is 20%~50% (w/w);
Step 3, the high temperature resistant bag is placed at temperature as 101 DEG C~108 DEG C, pressure is under 1.10MPa~1.15MPa, is protected
Press insulated sterilizing 30 minutes~60 minutes;
Step 4, treat that temperature is down to less than 50 DEG C, take out the high temperature resistant bag.
2. according to the method described in claim 1, it is characterized in that, further included before the step 1:
Low-density chitosan is made by shellfish, bulk density is 0.2g/ml~0.4g/ml;
High density chitosan is made in low-density chitosan processing, bulk density is more than 0.4g/ml.
3. according to the method described in claim 1, it is characterized in that, further included before the step 1:
It is compound prepared by chitosan molecule structure is modified or is modified.
4. according to the method described in claim 1, it is characterized in that, the mass ratio of water and ethanol is 1 in the step 1:0.1 to
1:0.4.
5. according to the method described in claim 1, it is characterized in that, chitosan or chitosan derivatives in the step 2
The mass percent of water-ethanol mixing liquid hold-up is 21%~27%.
6. according to the method described in claim 1, it is characterized in that, the step 3 by the high temperature resistant bag specifically, be placed in Sheng
On truck pallet, car is placed in the Sterilization Kettle of autoclaving equipment, controls 101 DEG C~108 DEG C of temperature, control pressure exists
1.10MPa~1.15MPa, pressure-maintaining and heat-preservation sterilize 30 minutes~60 minutes.
7. according to the method described in claim 1, it is characterized in that, temperature is 101 DEG C~105 DEG C in the step 3, pressure is
1.11MPa~1.14MPa.
8. according to the method described in claim 1, it is characterized in that, sterilization time is 45 minutes~60 minutes in the step 3.
9. according to the method described in claim 6, it is characterized in that, the step 4 is specifically, close the steaming of autoclaving equipment
Steam valve door, slowly pressure release, treats that the autoclaving equipment is cooled to less than 50 DEG C, takes out the high temperature resistant bag.
10. according to the method described in claim 1, it is characterized in that, the step 4 is specially:Temperature is down to 40 DEG C, takes out institute
State high temperature resistant bag.
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CN108570117A (en) * | 2017-03-13 | 2018-09-25 | 青岛博益特生物材料股份有限公司 | A kind of chitosan virus removal technique and its application |
CN109007172A (en) * | 2018-07-25 | 2018-12-18 | 黔西南州贵隆农业发展有限公司 | A kind of multi-functional pueraria lobata tea powder and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070093932A (en) * | 2007-08-06 | 2007-09-19 | 김순동 | Preparation method of deep sea water-chitosan dongchimi with functionality of hangover obliteration |
JP2009189274A (en) * | 2008-02-13 | 2009-08-27 | Sanei Gen Ffi Inc | Sterilizing-bacteriostatic agent |
CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
CN103014914A (en) * | 2011-09-26 | 2013-04-03 | 李永兴 | Method for preparing medical high-efficiency disinfected chitosan fibers by using disinfectant |
CN103864991A (en) * | 2014-02-07 | 2014-06-18 | 山东省泰和水处理有限公司 | Preparation method of chitosan grafted copolymer flocculation-bactericide |
-
2014
- 2014-12-18 CN CN201410794583.XA patent/CN105770941B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20070093932A (en) * | 2007-08-06 | 2007-09-19 | 김순동 | Preparation method of deep sea water-chitosan dongchimi with functionality of hangover obliteration |
JP2009189274A (en) * | 2008-02-13 | 2009-08-27 | Sanei Gen Ffi Inc | Sterilizing-bacteriostatic agent |
CN103014914A (en) * | 2011-09-26 | 2013-04-03 | 李永兴 | Method for preparing medical high-efficiency disinfected chitosan fibers by using disinfectant |
CN103012619A (en) * | 2013-01-11 | 2013-04-03 | 河北工业大学 | Water-soluble sulfonated/quaternized chitosan and preparation method thereof |
CN103864991A (en) * | 2014-02-07 | 2014-06-18 | 山东省泰和水处理有限公司 | Preparation method of chitosan grafted copolymer flocculation-bactericide |
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