CN110724208A - Anti-freezing carrageenan oligosaccharide and preparation method and application thereof - Google Patents
Anti-freezing carrageenan oligosaccharide and preparation method and application thereof Download PDFInfo
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- CN110724208A CN110724208A CN201911047667.6A CN201911047667A CN110724208A CN 110724208 A CN110724208 A CN 110724208A CN 201911047667 A CN201911047667 A CN 201911047667A CN 110724208 A CN110724208 A CN 110724208A
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- 229920001525 carrageenan Polymers 0.000 title claims abstract description 97
- 235000010418 carrageenan Nutrition 0.000 title claims abstract description 94
- 239000000679 carrageenan Substances 0.000 title claims abstract description 93
- 229940113118 carrageenan Drugs 0.000 title claims abstract description 93
- 229920001542 oligosaccharide Polymers 0.000 title claims abstract description 61
- -1 carrageenan oligosaccharide Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000007710 freezing Methods 0.000 title abstract description 7
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 239000012528 membrane Substances 0.000 claims abstract description 27
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 235000013305 food Nutrition 0.000 claims abstract description 5
- 239000002537 cosmetic Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 230000002528 anti-freeze Effects 0.000 claims description 13
- 238000001728 nano-filtration Methods 0.000 claims description 13
- 241001474374 Blennius Species 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 238000001694 spray drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004042 decolorization Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 235000013611 frozen food Nutrition 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000005185 salting out Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 13
- 150000002482 oligosaccharides Chemical class 0.000 abstract description 7
- 230000008014 freezing Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 4
- 241000206572 Rhodophyta Species 0.000 description 4
- ZNOZWUKQPJXOIG-XSBHQQIPSA-L [(2r,3s,4r,5r,6s)-6-[[(1r,3s,4r,5r,8s)-3,4-dihydroxy-2,6-dioxabicyclo[3.2.1]octan-8-yl]oxy]-4-[[(1r,3r,4r,5r,8s)-8-[(2s,3r,4r,5r,6r)-3,4-dihydroxy-6-(hydroxymethyl)-5-sulfonatooxyoxan-2-yl]oxy-4-hydroxy-2,6-dioxabicyclo[3.2.1]octan-3-yl]oxy]-5-hydroxy-2-( Chemical compound O[C@@H]1[C@@H](O)[C@@H](OS([O-])(=O)=O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H]2OC[C@H]1O[C@H](O[C@H]1[C@H]([C@@H](CO)O[C@@H](O[C@@H]3[C@@H]4OC[C@H]3O[C@H](O)[C@@H]4O)[C@@H]1O)OS([O-])(=O)=O)[C@@H]2O ZNOZWUKQPJXOIG-XSBHQQIPSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- 238000004457 water analysis Methods 0.000 description 4
- 241001428166 Eucheuma Species 0.000 description 3
- 101710184220 Kappa-carrageenase Proteins 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 description 3
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 241000940372 Eucheuma denticulatum Species 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 241000195474 Sargassum Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 125000000600 disaccharide group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 210000001723 extracellular space Anatomy 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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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
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0036—Galactans; Derivatives thereof
- C08B37/0042—Carragenan or carragen, i.e. D-galactose and 3,6-anhydro-D-galactose, both partially sulfated, e.g. from red algae Chondrus crispus or Gigantia stellata; kappa-Carragenan; iota-Carragenan; lambda-Carragenan; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/10—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives
- A23L33/125—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof using additives containing carbohydrate syrups; containing sugars; containing sugar alcohols; containing starch hydrolysates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/04—Disaccharides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/06—Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages
-
- 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
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Genetics & Genomics (AREA)
- Biotechnology (AREA)
- Nutrition Science (AREA)
- Food Science & Technology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Sustainable Development (AREA)
- Mycology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides freezing-resistant carrageenan oligosaccharide and a preparation method and application thereof, belonging to the technical field of industrial waste recycling and functional oligosaccharide preparation. The method fully utilizes the waste water generated in the carrageenan production process to extract the frost-resistant carrageenan oligosaccharide by using the membrane method, comprehensively develops the carrageenan production waste water, changes waste into valuable, reduces the sewage treatment difficulty, effectively reduces the production cost, has universality for different types of carrageenan oligosaccharides, and has application value in the fields of food, health care products, cosmetics and the like.
Description
Technical Field
The invention belongs to the technical field of industrial waste recycling and functional oligosaccharide preparation, and particularly relates to freezing-resistant carrageenan oligosaccharide and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Carrageenan (also called carrageenan and carrageenin) is a hydrophilic colloid extracted from red algae (Rhodophyta), and is a linear high molecular polysaccharide containing sulfate groups. The carrageenan desirably has a repeating α - (1 → 4) -D-galactopyranose- β - (1 → 3) -D-galactopyranose (or 3, 6-lacto-D-galactopyranose) disaccharide unit backbone structure.
The molecular weight of the carrageenan is more than 200,000Da, and the solubility is poor. The carrageenan oligosaccharide is a degradation product of carrageenan, has small molecular weight, good solubility and easy absorption, and meanwhile, the activity of the carrageenan oligosaccharide is obviously improved compared with that of the carrageenan because active groups in the molecular weight are fully exposed. Currently, carrageenan oligosaccharides are prepared by a physical method, a chemical method and an enzymatic hydrolysis method, wherein the enzymatic hydrolysis method is used most.
Chinese patent CN104894100A discloses an immobilized kappa-carrageenase and a method for preparing carrageenan oligosaccharide by using the same, firstly preparing the immobilized kappa-carrageenase, and then performing enzymolysis on the kappa-carrageenase to prepare the carrageenan oligosaccharide. Chinese patent CN103290079A discloses a method for preparing lambda-carrageenan oligosaccharide, which comprises the steps of firstly culturing degrading bacteria which can produce lambda-carrageenan degrading enzyme in the extracellular space, then adding bacteria liquid into lambda-carrageenan reaction liquid, and obtaining the carrageenan oligosaccharide through centrifugation, activated carbon adsorption, ethanol desorption, concentration and freeze drying after reaction. The process is complicated, the cost, particularly the freeze drying cost is high, and the industrial production is not convenient. Chinese patent CN106987574A discloses a method for preparing antioxidant kappa-carrageenan oligosaccharide by an enzyme method.
In summary, in the existing carrageenan oligosaccharides preparation technologies, carrageenan itself is used as a substrate, and the carrageenan molecules are degraded by an enzymolysis method, so that the substrate requirement is high, and different types of enzymes can only specifically degrade a certain carrageenan to obtain a specific type of carrageenan oligosaccharides (for example, kappa-carrageenan can only degrade kappa-carrageenan to obtain kappa-carrageenan oligosaccharides), and the preparation technologies have no universality. Meanwhile, a large amount of waste water is generated in the production process of the existing carrageenan, most of the waste water directly enters a reclaimed water treatment link, the sewage treatment cost is higher, and certain influence is caused on the environment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides freezing-resistant carrageenan oligosaccharide and a preparation method and application thereof. The method fully utilizes the waste water generated in the carrageenan production process to extract the carrageenan oligosaccharide by using the membrane method, comprehensively develops the carrageenan production waste water, changes waste into valuable, reduces the sewage treatment difficulty, effectively reduces the production cost, and has universality for different types of carrageenan oligosaccharides, thereby having good practical application value.
The invention provides a preparation method of freezing-resistant carrageenan oligosaccharide, which at least comprises the step of filtering carrageenan production waste liquid with a filter membrane to prepare the freezing-resistant carrageenan oligosaccharide.
Wherein the carrageenan production waste liquid is (a) and/or (b) as follows:
(a) the seaweed raw material is subjected to alkali treatment and water washing to generate washing waste liquid;
(b) the seaweed raw material is subjected to alkali treatment, water washing, gel boiling, filtering and gelling (salting out or alcohol precipitation), and then the carrageenin gel is dehydrated to generate filtrate;
the seaweed is a common raw material for extracting carrageenan, cell walls of the seaweed are removed by alkali treatment, after pectin in the seaweed is extracted, micromolecular oligosaccharide formed by molecular chain fracture in part of alkali treatment process still remains in an extracting solution, and therefore inorganic salt is removed by nanofiltration and the extracting solution is concentrated at the same time, and therefore the preparation of the carrageenan oligosaccharide product is realized.
The aperture of the filter membrane is 2-10nm, the filter membrane is preferably a polyamide nanofiltration membrane, the polyamide nanofiltration membrane below the aperture is adopted for continuous filtration and concentration, and meanwhile, small molecular salts and pigments are removed, so that concentrated solution is obtained;
wherein the pH value is controlled to be 10-12 in the alkali treatment process, and the alkali liquor treatment temperature is controlled to be 60-80 ℃; the ratio of the material to the liquid is controlled to be 1: 10-20;
meanwhile, it should be noted that, because the alkalinity of the washing waste liquid in (a) is too high, it is preferable to add acid to perform neutralization reaction, so as to reduce the pH of the washing waste liquid to be alkalescent (the pH is not higher than 8) or neutral, and then perform the subsequent preparation process.
In a second aspect of the invention, the antifreeze carrageenan oligosaccharide prepared by the preparation method is provided. The carrageenan oligosaccharide has the characteristics of good fluidity and difficult moisture absorption, the 10% solution still keeps the characteristics similar to Newtonian fluid, and the carrageenan oligosaccharide is heated, cooled and then cooled to form elastic gel which has excellent frost resistance and can be obtained by anhydrous analysis after being frozen at-18 ℃ for 72 hours.
In a third aspect of the invention, the antifreeze carrageenan oligosaccharide is applied to the fields of food, health care products or cosmetics, especially frozen food.
The invention has the beneficial technical effects that: the invention provides a method for extracting carrageenan oligosaccharide from wastewater in a carrageenan production process by using a membrane method, which comprehensively develops the carrageenan production wastewater, changes waste into valuable, reduces the sewage treatment difficulty, reduces the production cost of enterprises, and creates a new profit growth point.
The carrageenan oligosaccharide prepared by the invention has the characteristics of good fluidity, difficult moisture absorption and the like, and has excellent frost resistance, and meanwhile, the carrageenan oligosaccharide has universality for preparing different types (such as Kappa, Iota, Lamda and the like), so the carrageenan oligosaccharide has good practical application value.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described above, in the existing carrageenan oligosaccharides preparation technologies, carrageenan itself is used as a substrate, and carrageenan molecules are degraded by an enzymatic hydrolysis method, so that the requirement on the substrate is high, and different types of enzymes can only specifically degrade a certain kind of carrageenan to obtain a specific type of carrageenan oligosaccharides (for example, kappa-carrageenan can only degrade kappa-carrageenan to obtain kappa-carrageenan oligosaccharides), and the preparation technologies have no universality. Meanwhile, a large amount of waste water is generated in the production process of the existing carrageenan, most of the waste water directly enters a reclaimed water treatment link, the sewage treatment cost is higher, and certain influence is caused on the environment.
In view of the above, in one embodiment of the present invention, a method for preparing antifreeze carrageenan oligosaccharides is provided, the method at least comprises the step of filtering carrageenan production waste liquid with a filter membrane to prepare the antifreeze carrageenan oligosaccharides.
In another embodiment of the present invention, the carrageenan production waste liquid is (a) and/or (b) below:
(a) the seaweed raw material is subjected to alkali treatment and water washing to generate washing waste liquid;
(b) the seaweed raw material is subjected to alkali treatment, water washing, gel boiling, filtering and gelling (salting out or alcohol precipitation), and then the carrageenin gel is dehydrated to generate filtrate;
in another embodiment of the present invention, the seaweed material is red algae (Rhodophyta), and more preferably Eucheuma cottonii (Eucheuma cottonii) or Eucheuma spinosum (Eucheuma spinosum), and the seaweed is a common raw material for extracting carrageenan, and after the pectin in the seaweed is extracted, the small molecular oligosaccharide formed by molecular chain breakage in the process of partial alkali treatment still remains in the extract, so that the inorganic salt is removed by nanofiltration and the extract is concentrated, thereby realizing the preparation of the carrageenan oligosaccharide product.
In another embodiment of the invention, the aperture of the filter membrane is 2-10nm, the filter membrane is preferably a polyamide nanofiltration membrane, and the polyamide nanofiltration membrane below the aperture is used for continuous filtration and concentration, and simultaneously small molecular salts and pigments are removed to obtain a concentrated solution;
in another embodiment of the invention, the pH value is controlled to be 10-12 in the alkali treatment process, and the alkali liquor treatment temperature is controlled to be 60-80 ℃; the ratio of the material to the liquid is controlled to be 1: 10-20;
meanwhile, it should be noted that, because the alkalinity of the washing waste liquid in (a) is too high, acid is preferably added for neutralization reaction, so that the pH of the washing waste liquid is reduced to alkalescence (the pH is not higher than 8) or neutrality, and then the subsequent preparation process is carried out;
in yet another embodiment of the invention, the concentrate has a soluble solids content of no greater than 10 Bx;
in another embodiment of the present invention, the carrageenan oligosaccharide is obtained by decoloring and spray drying the concentrated solution.
In another embodiment of the present invention, the decoloring is performed by an activated carbon decoloring method, and the decoloring effect is good, and further, the decoloring process includes: heating the concentrated solution to 60-80 ℃ (preferably 70 ℃) for active carbon decolorization, wherein the time of decolorization treatment is controlled to be 30-60 min (preferably 40 min);
in another embodiment of the present invention, the spray drying method comprises: and (3) carrying out spray drying treatment on the decolorized concentrated solution, controlling the feeding pressure to be 18-25 bar (preferably 20bar), and controlling the air inlet temperature to be 160-180 ℃ (preferably 170 ℃).
In another embodiment of the present invention, in the actual production, a concentration step may be added between the decoloring and spray drying steps according to the actual production conditions, so as to facilitate the subsequent spray drying process.
In another embodiment of the invention, the antifreeze carrageenan oligosaccharide prepared by the preparation method is provided. The molecular weight of the carrageenan oligosaccharide prepared by the invention is 5000-10000Da, the steric hindrance is small, and more hydroxyl groups are exposed, so that intermolecular hydrogen bonds are more easily formed with water molecules to play a role in water retention. Therefore, the carrageenan oligosaccharide has the advantages of good fluidity, difficult moisture absorption and the like, the 10% solution still keeps the characteristics similar to Newtonian fluid, the elastic gel is formed by cooling after heating and cooling, has excellent frost resistance, and can be frozen at-18 ℃ for 72h without water analysis.
In a third aspect of the invention, the antifreeze carrageenan oligosaccharide is applied to the fields of food, health care products or cosmetics, especially frozen food.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions. In each example, the carrageenan extraction process is a conventional carrageenan extraction process, and specifically comprises the following steps: processing Sargassum (Eucheuma cottonii) with alkali, washing with water, decocting, filtering with plate and frame, precipitating with ethanol to obtain gel, press-filtering with diaphragm, shredding, drying, and pulverizing to obtain refined carrageenan; wherein the pH value in the alkali treatment process is controlled to be 10, and the alkali treatment temperature is controlled to be 80 ℃; the ratio of the feed to the liquid is controlled to be 1: 15.
Example 1
A preparation method of antifreeze carrageenan oligosaccharides comprises the following steps:
(1) adding acid to neutralize the water washing waste liquid generated in the water washing step in the carrageenan extraction process until the pH value is neutral, and collecting the water washing waste liquid in a stirring device and a temporary storage tank;
(2) pumping the washing waste liquid treated in the step (1) into a nanofiltration operation system (the used filter membrane is a polyamide nanofiltration membrane, the aperture of the filter membrane is 4nm) through a series-connected double-seal centrifugal pump and a multistage centrifugal booster pump, and continuously concentrating until the content of soluble solids is 10 Bx;
(3) heating the concentrated solution to 70 deg.C by plate heat exchanger, placing in a decolorizing tank with activated carbon, and decolorizing for 40 min;
(4) pumping the further treated concentrated solution into a spray drying tower by a high-pressure pump, wherein the feeding pressure is 20bar, and the air inlet temperature is 170 ℃;
(5) granulating the spray-dried product by a fluidized bed to obtain the final product of carrageenan oligosaccharide.
The carrageenan oligosaccharide has the characteristics of good fluidity and difficult moisture absorption, the 10% solution still keeps the characteristics similar to Newtonian fluid, and the carrageenan oligosaccharide forms elastic gel after being heated and cooled, has excellent frost resistance, and can be obtained after being frozen at the temperature of minus 18 ℃ for 72 hours without water analysis.
Example 2
A preparation method of antifreeze carrageenan oligosaccharides comprises the following steps:
(1) collecting filtrate generated by diaphragm filter pressing in a carrageenan extraction process in a stirring device and a temporary storage tank;
(2) pumping the filtrate into a nanofiltration operation system (the used filter membrane is a polyamide nanofiltration membrane, the aperture of the filter membrane is 8nm) through a series-connected double-seal centrifugal pump and a multistage centrifugal booster pump, and continuously concentrating the filtrate until the content of soluble solids is 8Bx, wherein the feed pressure is 10 bar;
(3) heating the concentrated solution to 80 deg.C by plate heat exchanger, placing in a decolorizing tank with activated carbon, and decolorizing for 40 min;
(4) pumping the further treated concentrated solution into a spray drying tower by a high-pressure pump, wherein the feeding pressure is 20bar, and the air inlet temperature is 180 ℃;
(5) granulating the spray-dried product by a fluidized bed to obtain the final product of carrageenan oligosaccharide.
The carrageenan oligosaccharide has the characteristics of good fluidity and difficult moisture absorption, the 10% solution still keeps the characteristics similar to Newtonian fluid, and the carrageenan oligosaccharide forms elastic gel after being heated and cooled, has excellent frost resistance, and can be obtained after being frozen at the temperature of minus 18 ℃ for 72 hours without water analysis.
Example 3
A preparation method of antifreeze carrageenan oligosaccharides comprises the following steps:
(1) collecting the production wastewater in the carrageenan extraction process in a stirring device and a temporary storage tank;
the production wastewater is mixed wastewater of water washing waste liquid generated in the water washing step and filtrate generated by diaphragm filter pressing, wherein the ratio of the water washing waste liquid to the filtrate is 1: 1.
(2) Pumping the filtrate into a nanofiltration operation system (the used filter membrane is a polyamide nanofiltration membrane, the aperture of the filter membrane is 5nm) through a series-connected double-seal centrifugal pump and a multistage centrifugal booster pump, and continuously concentrating the filtrate until the content of soluble solids is 9Bx, wherein the feed pressure is 10 bar;
(3) heating the concentrated solution to 70 deg.C by plate heat exchanger, placing in a decolorizing tank with activated carbon, and decolorizing for 40 min;
(4) the concentrated solution after decolorization is concentrated under normal pressure and then is pumped into a spray drying tower through a high-pressure pump, the feeding pressure is 20bar, and the air inlet temperature is 160 ℃;
(5) granulating the spray-dried product by a fluidized bed to obtain the final product of carrageenan oligosaccharide.
The carrageenan oligosaccharide has the characteristics of good fluidity and difficult moisture absorption, the 10% solution still keeps the characteristics similar to Newtonian fluid, and the carrageenan oligosaccharide forms elastic gel after being heated and cooled, has excellent frost resistance, and can be obtained after being frozen at the temperature of minus 18 ℃ for 72 hours without water analysis.
It should be noted that the above examples are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the examples given, those skilled in the art can modify the technical solution of the present invention as needed or equivalent substitutions without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the antifreeze carrageenan oligosaccharide is characterized by at least adopting carrageenan production waste liquid to filter by a filter membrane to prepare the antifreeze carrageenan oligosaccharide.
2. The preparation method according to claim 1, wherein the carrageenan production waste liquid is (a) and/or (b) as follows:
(a) the seaweed raw material is subjected to alkali treatment and water washing to generate washing waste liquid;
(b) the seaweed raw material is subjected to alkali treatment, water washing, gel boiling, filtering and gelling (salting out or alcohol precipitation), and then the carrageenin gel is dehydrated to generate filtrate;
preferably, the pH value is controlled to be 10-12 in the alkali treatment process, and the alkali liquor treatment temperature is controlled to be 60-80 ℃; the ratio of the material to the liquid is controlled to be 1: 10-20;
preferably, the water washing waste liquid in (a) is treated by adding acid, so that the pH of the water washing waste liquid is reduced to alkalescence (the pH is not higher than 8) or neutrality.
3. The method of claim 1, wherein the pore size of the filter membrane is 2-10nm, and the filter membrane is preferably a polyamide nanofiltration membrane.
4. The method of claim 1, wherein the concentrate after filtration through the membrane has a soluble solids content of no greater than 10 Bx.
5. The preparation method according to claim 1, wherein the carrageenan oligosaccharide is obtained by decoloring and spray drying the filtrate; or the like, or, alternatively,
and decoloring, concentrating and spray drying the filtrate to obtain the carrageenan oligosaccharide.
6. The method according to claim 5, wherein the decolorization is performed by activated carbon decolorization.
7. The method according to claim 6, wherein the decoloring process is: and heating the concentrated solution to 60-80 ℃ (preferably 70 ℃) for active carbon decolorization, wherein the time for decolorization treatment is controlled to be 30-60 min (preferably 40 min).
8. The preparation method according to claim 1, wherein the spray drying is carried out by a specific treatment method comprising: and (3) carrying out spray drying treatment on the decolorized concentrated solution, controlling the feeding pressure to be 18-25 bar (preferably 20bar), and controlling the air inlet temperature to be 160-180 ℃ (preferably 170 ℃).
9. Antifreeze carrageenan oligosaccharides prepared by the preparation method of any one of claims 1 to 8.
10. Use of antifreeze carrageenan oligosaccharides according to claim 9 in the field of food, health products or cosmetics; preferably, the food product is a frozen food product.
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