CN105504086B - A kind of preparation method of food-grade calcium alginate - Google Patents
A kind of preparation method of food-grade calcium alginate Download PDFInfo
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- CN105504086B CN105504086B CN201510906222.4A CN201510906222A CN105504086B CN 105504086 B CN105504086 B CN 105504086B CN 201510906222 A CN201510906222 A CN 201510906222A CN 105504086 B CN105504086 B CN 105504086B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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Abstract
The invention discloses a kind of preparation methods of food-grade calcium alginate, include the following steps：Brown alga is embathed plus sodium carbonate digestion extraction alginic acid；Dilution, filtering；Dissolved air flotation；Essence filtering；Logical bleaching by chlorine gas；Calcium chloride solution is added, water soluble algae acid sodium is converted to water-insoluble calcium alginate；Washing；Dehydration；Dry, crushing.Polishing diatomaceous filtration is added in the present invention, eliminates the harmful substances such as pigment, heavy metal, produces the calcium alginate for reaching food-grade requirement, can be widely used for the industries such as medicine, food, daily use chemicals.
Description
Technical field
The invention belongs to prepare the technical field of calcium alginate, more particularly to a kind of preparation side of food-grade calcium alginate
Method.
Background technology
Alginate is a kind of natural polysaccharide extracted from the brown algas such as kelp, sargassum, bulk kelp, yellow tang, commonly uses sea
Alginates are the water-soluble algins such as sodium alginate, potassium alginate, and calcium alginate is a kind of alginate of water-insoluble,
With good edible safety, gelling thickener, calcium tonic etc. are can be used as, in countries such as Japan, Russia, European Union, the U.S.
It has been put into food additives, it is domestic from 2016 calcium alginate to be allowed as food additives application.Utilize calcium alginate
Meet it is water-dispersed, plus alkali or salt dissolving characteristic be widely used in the industries such as medicine, food, chemical industry, play aqueous colloidal suspending,
The functions such as thick stabilization, emulsification, film forming, sustained release.
The country is using the intermediate product of calcification technique as calcium alginate product at present, product heavy metal, inorganic salts residual
Height is only used for industry；Foreign countries are prepared using Japanese FMC as the alginates manufacturing enterprise of representative using alginic acid in acidization technique
Calcium alginate, product purity is high, but technique is cumbersome and generates the waste liquids such as sour water.
Chen Hong et al. discloses a kind of production method of high-quality calcium alginate in patent (103333271 A of CN).It should
Production method is " the acidified generation alginic acid of sodium alginate for preparing brown alga；Alginic acid is using ethyl alcohol, propyl alcohol, ethyl acetate
It is cleaned 2-4 times with the complex cleaning and washing agent of water composition；Alginic acid after cleaning occurs neutralization reaction with calcium source by medium using water and is made
Calcium alginate ".The preparation method is similar to the acidization that foreign countries use, and introduces other organic solvents in the reaction, makes finished product
Reach food quality requirement, but technique is cumbersome, it is of high cost.
Liu Jun rosy clouds et al. disclose a kind of preparation method of calcium alginate in patent (102977224 A of CN).The preparation
Method is " to extract alginic acid after brown alga is embathed plus soda ash digestion, the calcification of addition calcium preparation, acidification；It washs and is dehydrated；It is granulated；It is cold
Agar is broken；Calcium preparation calcification is added；Dehydration；It is dry；It crushes ".Calcium is added in the sodium alginate that will be extracted from brown alga in this method
Acidification extraction alginic acid after preparation calcification, is then granulated, calcium preparation calcification, dehydration, drying, technique is added again after Freezing smashing
More complicated, cost higher.
Invention content
The present invention removes depigmentation, again by the way that kieselguhr adsorption drainage is added in the sodium alginate soln after dissolved air flotation
The harmful substances such as metal；A certain amount of chlorine is passed through in sodium alginate and calcium chloride solution mixed process, it is not only simple for process, it is raw
Produce it is at low cost, while can effectively inhibit calcium alginate molecule cross-link structure cooperating microorganisms and improve product color, reach food
The requirement of safety.
For achieving the above object, the present invention is achieved using following technical proposals：A kind of food-grade calcium alginate
Preparation method, which is characterized in that step is：1) prepared by sodium alginate：Brown alga is embathed plus sodium carbonate carries out digestion reaction, adds
Clarification sodium alginate soln is obtained by filtration in water dilution；2) sodium alginate purifies：Kieselguhr adsorption is added in sodium alginate soln
Drainage；3) it filters：Clarification glue is obtained by filtration in sodium alginate and diatomaceous mixed liquor essence；4) glue is bleached：Chlorine is passed through,
Bleach glue；5) prepared by calcium alginate：Calcium chloride solution is added in above-mentioned clarification glue, water-soluble sodium alginate is made to change
Precipitation is concentrated for the calcium alginate gel of water-insoluble；6) post-processing：Washing, dehydration, dry, crushing, obtain food-grade
Calcium alginate.
Further, the brown alga in the step 1) is one or more of kelp, bulk kelp, yellow tang, sargassum.
Further, digestion reaction temperature is 40-60 DEG C in the step 1), reaction time 4-8h.
Further, sodium carbonate addition is brown alga quality 20-30% in the step 1).
Further, diatomaceous in the step 2) that the 1-5 ‰ that quality is sodium alginate soln quality is added.
Further, essence filters the filter type using press filtration or vacuum filtration in the step 3).
Further, the amount of chlorine being passed through in the step 4) is 1-4m3/h。
Further, the mass concentration of calcium chloride solution is 10-15% in the step 5), and the amount of calcium chloride solution is added
For the 2-4% of glue volume.
Further, in the step 6), dehydration to Han Shui Liang≤70% is dry to Han Shui Liang≤15%.
Compared with prior art, the advantages and positive effects of the present invention are：
1, the present invention has been adsorbed the impurity such as pigment, the heavy metal in alginate solution, has been improved eventually by the way that diatomite is added
The quality of product calcium alginate.Sodium alginate through diatomite after purification can directly use calcification technique, be converted into
Calcium alginate shortens technological process, reduces production cost, reduces the discharge of waste liquid.
2, the present invention is passed through chlorine in sodium alginate soln, and reducing calcium alginate leads to product shape because of microbial degradation
Shape changes, and ensure that microbiological indicator meets food-grade requirement in finished product.Simultaneously because the blanching effect of chlorine, it can be apparent
Improve the color and luster of finished product, improves product quality.
Specific implementation mode
The present invention provides a kind of preparation methods of food-grade calcium alginate, and steps are as follows：
1) sodium alginate is prepared：Brown alga is washed in the water logging that addition is equivalent to dry 6-10 times of brown alga weight；Dry brown alga quality is added
The sodium carbonate of 20-30% carries out digestion reaction 4-8h at 40-60 DEG C, obtains sodium alginate；With being equivalent to dry brown alga quality 80-
120 times of water dilutes glue；Dissolved air flotation obtains clarification sodium alginate soln；The wherein described brown alga is kelp, bulk kelp, bubble leaf
One or more of algae, sargassum.
2) sodium alginate purifies：Kieselguhr adsorption drainage is added in above-mentioned clarification sodium alginate soln；The diatomite
Addition quality be sodium alginate soln quality 1-5 ‰, diatomite mesh number be 50-200 mesh (model is preferably emerging brightness SY-
RS600).Diatomite, which is added, can adsorb the impurity such as pigment, heavy metal in alginate solution, improve finished product calcium alginate
Quality, meet food grade standard.
3) it filters：Sodium alginate and diatomaceous mixed liquor are subjected to smart filtering, removal has been adsorbed the diatomite of impurity, obtained
To clarification glue；Smart filtering is carried out using modes such as press filtration or vacuum filtrations.
4) glue is bleached：It is passed through 1-4m in above-mentioned clarification glue3/ h chlorine；Glue is bleached, for improving end
The color and luster of product, reduce calcium alginate causes shape of product to change because of microbial degradation, and ensure that microorganism in finished product
Index meets food-grade requirement.
5) prepared by calcium alginate：Calcium chloride solution is added in glue after above-mentioned bleaching, makes water-soluble sodium alginate
It is changed into the calcium alginate gel of water-insoluble and concentrates precipitation, the amount that calcium chloride solution is added is the 2-4% of glue volume, chlorine
The mass concentration for changing calcium solution is 10-15%.
6) post-processing：Add water washing calcium alginate gel, dehydration to Han Shui Liang≤70%, it is dry to Han Shui Liang≤
15%, it is crushed to granularity 100% and sieves with 100 mesh sieve, 70% crosses 200 mesh sieve.Obtain final product food-grade calcium alginate.
Raw material and auxiliary agent used in the method for the present invention are all made of food grade standard.
Final product calcium alginate prepared by the present invention is creamy white, lead content≤4mg/kg, and arsenic content≤2mg/kg, chlorine contains
Amount≤0.1mg/kg, microbial count≤1000cfu/g, CaO content 12.0-13.0% meet food grade standard, can be used for curing
The top grade production such as medicine, food, daily use chemicals, improves added value of product.
Embodiment 1
The preparation method of calcium alginate of the present invention includes the following steps：
1, kelp embathes and digests：Kelp is washed into 12h with water logging, then adds the sodium carbonate of dry kelp quality 20%, 40
DEG C heat preservation digestion 5h after, kelp is smashed with mechanical agitation；The water dilution glue for being equivalent to 100 times of dry kelp raw material weight is added
Liquid obtains clear sodium alginate soln after dissolved air flotation；
2, sodium alginate purifies：The diatomite of solution quality 1.3 ‰ is added into sodium alginate soln, diatomite mesh number is
100 mesh (the emerging brightness SY-RS600 of model)；
3, it filters：By plate-frame filtering clarification glue is arrived by what sodium alginate and diatomaceous mixed liquor detached；
4, it bleaches：1m is passed through in glue3/ h chlorine bleaches glue.
5, prepared by calcium alginate：The calcium chloride solution that mass concentration is 13%, chlorine are added into the glue after above-mentioned bleaching
The amount for changing calcium solution is the 2.3% of glue volume, and water-soluble seaweed acid solution is become to the calcium alginate gel of water-insoluble；
6, post-processing：Add water washing calcium alginate gel, and is dehydrated to water content ＜ 70% using expeller device；
7, calcium alginate is dried to by Han Shui Liang≤15% using boiling-bed drying, is crushed to granularity 100% and crosses 100 mesh,
70% crosses 200 mesh, obtains calcium alginate product.
The experimental result of gained calcium alginate product：Moisture content 11.2%, total number of bacteria≤1000cfu/g, mould, saccharomycete
Sum≤100cfu/g, lead content 3.8mg/kg, arsenic 1.9mg/kg, chlorinity 0.09mg/kg, CaO content 12.1%.
Embodiment 2
1, kelp embathes and digests：Kelp is washed into 12h with water logging, then adds the sodium carbonate of dry kelp quality 23%, 50
DEG C heat preservation digestion 4h after, kelp is smashed with mechanical agitation；The water dilution glue for being equivalent to 100 times of dry kelp raw material weight is added
Liquid obtains clear sodium alginate soln after dissolved air flotation.
2, sodium alginate purifies：The diatomite of glue quality 2.0 ‰ is added into sodium alginate soln, diatomite mesh number is
100 mesh (the emerging brightness SY-RS600 of model).
3, it filters：By being filtered by vacuum sodium alginate and the isolated clarification glue of diatomaceous mixed liquor.
4, it bleaches：Glue is bleached：It is passed through 1.2m3/ h chlorine bleaches glue.
5, prepared by calcium alginate：The calcium chloride solution that mass concentration is 14%, the amount of calcium chloride solution are added into glue
It is the 2.1% of glue volume, water-soluble seaweed acid solution is become to the calcium alginate gel of water-insoluble.
6, post-processing：Add water washing calcium alginate gel, and is dehydrated to water content ＜ 70% using expeller device.
7, calcium alginate is dried to by Han Shui Liang≤15% using boiling-bed drying, is crushed to granularity 100% and crosses 100 mesh,
70% crosses 200 mesh, obtains calcium alginate product.
The experimental result of gained calcium alginate：Moisture content 10.0%, total number of bacteria≤1000cfu/g, mould, saccharomycete sum
≤ 100cfu/g, lead content 3.6mg/kg, arsenic 1.7mg/kg, chlorinity 0.08mg/kg, CaO content 12.3%
Embodiment 3
1, bulk kelp embathes and digests：Bulk kelp is washed for 24 hours with water logging, then the sodium carbonate of addition bulk kelp quality 26%, 55 DEG C
After heat preservation digestion 8h, bulk kelp is smashed with mechanical agitation；The water dilution glue for being equivalent to 100 times of dry kelp raw material weight is added,
Clear sodium alginate soln is obtained after dissolved air flotation.
2, sodium alginate purifies：The diatomite of glue quality 2.2 ‰ is added into sodium alginate soln, diatomite mesh number is
100 mesh (the emerging brightness SY-RS600 of model)
3, it filters：By being filtered by vacuum sodium alginate and the isolated clarification glue of diatomaceous mixed liquor.
4, it bleaches：Glue is bleached：It is passed through 2.1m3/ h chlorine bleaches glue.
5, prepared by calcium alginate：The calcium chloride solution that mass concentration is 15%, the amount of calcium chloride solution are added into glue
It is the 2.5% of glue volume, water-soluble seaweed acid solution is become to the calcium alginate gel of water-insoluble.
6, post-processing：Add water washing calcium alginate gel, and is dehydrated to water content ＜ 70% using expeller device.
7, calcium alginate is dried to by Han Shui Liang≤15% using boiling-bed drying, is crushed to granularity 100% and crosses 100 mesh,
70% crosses 200 mesh, obtains calcium alginate product.
The experimental result of gained calcium alginate：Moisture content 12.0%, total number of bacteria≤1000cfu/g, mould, saccharomycete sum
≤ 100cfu/g, lead content 2.5mg/kg, arsenic 1.6mg/kg, chlorinity 0.09mg/kg, CaO content 12.0%.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than is limited；Although with reference to aforementioned reality
Applying example, invention is explained in detail, for those of ordinary skill in the art, still can be to aforementioned implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features；And these are changed or replace
It changes, the spirit and scope for claimed technical solution of the invention that it does not separate the essence of the corresponding technical solution.
Claims (1)
1. a kind of preparation method of food-grade calcium alginate, which is characterized in that include the following steps：
1）Prepare sodium alginate：Brown alga is washed in the water logging that addition is equivalent to dry 6-10 times of brown alga weight, and dry brown alga quality 20- is added
30% sodium carbonate carries out digestion reaction 4-8h at 40-60 DEG C, obtains sodium alginate, with being equivalent to dry 80-120 times of brown alga quality
Water dilute glue, dissolved air flotation obtain clarification sodium alginate soln, wherein the brown alga be kelp, bulk kelp, yellow tang, horse
One or more of tail algae；
2）Sodium alginate purifies：In step 1）Gained, which is clarified, is added kieselguhr adsorption drainage, the diatom in sodium alginate soln
The addition quality of soil is the 1-5 ‰ of sodium alginate soln quality, and diatomite mesh number is 50-200 mesh, the emerging brightness SY- of model
RS600；
3）Filtering：Sodium alginate and diatomaceous mixed liquor are subjected to smart filtering, removal has been adsorbed the diatomite of impurity, obtained clear
Clear glue solution carries out smart filtering by the way of press filtration or vacuum filtration；
4）Glue is bleached：In step 3）It is passed through 1-4m3/h chlorine in gained clarification glue, glue is bleached；
5）It is prepared by calcium alginate：In step 4）Calcium chloride solution is added in glue after bleaching, water-soluble sodium alginate is made to turn
Become the calcium alginate gel of water-insoluble and concentrate precipitation, the amount that calcium chloride solution is added is the 2-4% of glue volume, chlorination
The mass concentration of calcium solution is 10-15%；
6）Post-processing：Add water washing calcium alginate gel, dehydration to Han Shui Liang≤70% is dry to Han Shui Liang≤15%, crushes
It is sieved with 100 mesh sieve to granularity 100%, 70% crosses 200 mesh sieve, obtains final product food-grade calcium alginate；Raw material and auxiliary agent used is equal
Using food grade standard.
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| CN106674373B (en) * | 2016-12-14 | 2019-09-13 | 青岛明月海藻集团有限公司 | A kind of extracting method and waste Ca water reuse method of alginate |
| CN108210978A (en) * | 2017-11-21 | 2018-06-29 | 青岛明月海藻集团有限公司 | A kind of calcium alginate non-woven fabrics and preparation method thereof |
| CN108659143B (en) * | 2018-06-14 | 2020-09-11 | 青岛海之林生物科技开发有限公司 | Green extraction and purification process of algin |
| CN110862561B (en) * | 2019-11-19 | 2022-11-11 | 青岛明月藻酸盐组织工程材料有限公司 | Preparation method of water-insoluble alginate for in vivo implantation |
| CN114532463B (en) * | 2022-03-08 | 2023-12-22 | 渤海水产股份有限公司 | Seaweed compound, preparation method and application thereof, and fish-farming feed |
| CN114700046A (en) * | 2022-03-31 | 2022-07-05 | 华南理工大学 | Crystal violet dye adsorption hydrogel microspheres and preparation method and application thereof |
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| CN101585890B (en) * | 2008-06-20 | 2011-08-24 | 青岛聚大洋海藻工业有限公司 | Method for preparing sodium alginate from kelp |
| CN101735333A (en) * | 2009-12-31 | 2010-06-16 | 庞作斌 | Method for preparing high-quality sodium alginate |
| CN102060938B (en) * | 2010-12-24 | 2012-10-17 | 青岛明月海藻集团有限公司 | Method for extracting algin through comprehensively utilizing brown algae |
| CN102718884B (en) * | 2011-11-29 | 2015-09-02 | 青岛聚大洋藻业集团有限公司 | A kind of method adopting fresh Sargassum fusiforme to extract algin |
| CN103613683A (en) * | 2013-11-30 | 2014-03-05 | 青岛海之林生物科技开发有限公司 | Method for extracting sodium alginate from gulfweed |
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