CN110357978A - A kind of preparation method of selenide of carragheen - Google Patents
A kind of preparation method of selenide of carragheen Download PDFInfo
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- CN110357978A CN110357978A CN201810317576.9A CN201810317576A CN110357978A CN 110357978 A CN110357978 A CN 110357978A CN 201810317576 A CN201810317576 A CN 201810317576A CN 110357978 A CN110357978 A CN 110357978A
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- carragheen
- selenide
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- 241000206575 Chondrus crispus Species 0.000 title claims abstract description 78
- 150000003346 selenoethers Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 18
- 230000001376 precipitating effect Effects 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002774 Maltodextrin Polymers 0.000 claims abstract description 8
- 239000005913 Maltodextrin Substances 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 8
- 229940035034 maltodextrin Drugs 0.000 claims abstract description 8
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 small molecule selenide Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 229920002521 macromolecule Polymers 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 239000005457 ice water Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229920001525 carrageenan Polymers 0.000 claims description 12
- 239000000679 carrageenan Substances 0.000 claims description 12
- 229940113118 carrageenan Drugs 0.000 claims description 12
- 235000010418 carrageenan Nutrition 0.000 claims description 12
- 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 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001728 nano-filtration Methods 0.000 claims description 8
- 238000000108 ultra-filtration Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229940082569 selenite Drugs 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001626 barium chloride Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- MCAHWIHFGHIESP-UHFFFAOYSA-L selenite(2-) Chemical compound [O-][Se]([O-])=O MCAHWIHFGHIESP-UHFFFAOYSA-L 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 238000005507 spraying Methods 0.000 claims 1
- 230000005428 wave function Effects 0.000 claims 1
- 238000001694 spray drying Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 27
- 229910052711 selenium Inorganic materials 0.000 description 24
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 22
- 229940091258 selenium supplement Drugs 0.000 description 21
- 239000000047 product Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000012043 crude product Substances 0.000 description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 8
- 229960001471 sodium selenite Drugs 0.000 description 8
- 239000011781 sodium selenite Substances 0.000 description 8
- 235000015921 sodium selenite Nutrition 0.000 description 8
- 206010039921 Selenium deficiency Diseases 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 5
- 239000005017 polysaccharide Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- 240000000233 Melia azedarach Species 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012869 ethanol precipitation Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011785 micronutrient Substances 0.000 description 1
- 235000013369 micronutrients Nutrition 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229960002668 sodium chloride Drugs 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- A23L33/16—Inorganic salts, minerals or trace elements
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Molecular Biology (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mycology (AREA)
- Nutrition Science (AREA)
- Food Science & Technology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of preparation methods of selenide of carragheen, the following steps are included: carragheen ultrasonic degradation under the conditions of acid ice-water bath, barium ions or calcium ion catalysis under with selenous acid or its reactant salt, sodium sulphate precipitating is added and removes barium ions or calcium ion, by separation UF membrane after in tune, it is eventually adding maltodextrin spray drying and selenide of carragheen powder is made.Ultrasonic degradation carragheen in the present invention, more rapidly, mildly, environmental protection；Seperation film filtering is more efficient, environmentally protective to separate organic macromolecule selenide of carragheen and small molecule selenide of carragheen and other inorganic substances；The use of spray drying keeps powder size more uniform, and production link is relatively sanitary, and product degree of purity is high.
Description
Technical field
The present invention relates to a kind of preparation method of selenizing polysaccharide compound, in particular to a kind of preparation of selenide of carragheen
Method belongs to the preparation of marine polysaccharide class compound and separation technology field.
Background technique
Selenium is one of micronutrient element necessary to humans and animals, have remove free radical, it is anti-oxidant (be vitamin E
50-500 times), inhibit lipid peroxide to generate, the enhancing multiple biological activities such as immune function.According to statistics, the whole world has more than 40
Countries and regions selenium deficiency, China are the areas of selenium deficiency most serious in the world, and the province of selenium deficiency accounts for about the 72% of national total area,
In 30% be serious selenium deficiency area.Some areas of 22 provinces and cities, China, about 700,000,000 people live in low selenium band.Chinese territory face
Product belongs to low selenium or selenium deficiency soil, and crops depend on the form and its effectively of selenium to the degree of absorption for being present in selenium in soil in addition
Property, most of selenium are existed with habit, it is difficult to be absorbed by crops utilization, this just restricts the battalion of selenium in Chinese food
The situation of supporting.And selemium nutrition element lacks the generation that will lead to many diseases of humans and animals.
Selenium source is divided into two class of inorganic selenium and organic selenium at present.Inorganic selenium main representative is selenous acid, and organic selenium includes ferment
Female selenium and selenide of carragheen etc..Compared with inorganic selenium, organic selenium has high biological absorption, high bioavailability and hypotoxicity etc.
Feature, thus organic selenium just gradually replaces inorganic selenium to become novel selemium nutrition agent.Organic selenium source of research safety health, with supplement
Human body lives in the general level of the health of selenium deficiency Area Inhabitants with very great meaning for raising to the intake of selenium.
Selenide of carragheen be one kind with carragheen, selenous acid or its salt etc. for raw material, the reacted and food that is refining to obtain
Nutrition fortifier is widely used in food and field of health care food at present, due to its excellent physico-chemical property and curative effect, it is believed that its
Will also there be good development in future in agricultural, field of fodder.
Currently, the patent of the production method about selenide of carragheen is not also very much, such as application No. is CN88103347
Chinese patent disclose a kind of preparation method of selenide of carragheen: after first dissolving selenium powder with concentrated nitric acid, then carragheen is added
Heating stirring in sodium-chloride water solution forms uniform carrageenan sol；Above two solution is reacted under certain condition, it will
Reaction solution ethyl alcohol precipitating, re-dry crush.The Chinese patent of Publication No. CN1288899A discloses a kind of selenizing polysaccharide
Close object and preparation method thereof: polysaccharide compound, selenous acid or its salt, barium ions, hydrogen ion is anti-under certain condition together
It answers, obtains selenium compound of polysaccharide；It adds sulfuric acid solution and removes barium ions, ferric chloride solution, NH is added3-NH4HCl solution removes
Remove unreacted selenite radical ion；After adjusting pH with sodium acetate, with ethanol precipitation, drying purification is filtered.Both the above
The selenide of carragheen Se content of method preparation is lower, while introducing excessive other elements and group during the preparation process, can
Contain harmful element in the product that can make, is finally separating purifying process and uses ethanol precipitation, dry refinement treatment
Mode causes organic substance to separate with inorganic substances and is not thorough, and makes the of low quality of final products.
It dialyses to obtain selenide of carragheen oligosaccharides with the bag filter that molecular cut off is 500 in addition, also having and mentioning in document, but
Its retention yield is low, and the selenide of carragheen Se content of preparation is low, and if there are the undegradable selenium for crossing macromolecule in product
Change OK a karaoke club film segment, influence will cause on the application of later product, such as be difficult to dissolve in clinical use and absorb.
Summary of the invention
In order to solve the shortcoming of existing technology, the object of the present invention is to provide a kind of green, environmental protection, efficient selenium
Change the preparation method of carragheen, while prepared product purity is high, it is high-quality.
The method of the present invention includes following steps:
(1) carragheen degrade: by carragheen be dissolved in water be made into mass concentration be 0.5%-4% solution after, be added acetic acid adjust it is molten
Liquid pH value controls temperature under ice-water bath and utilizes ultrasonic degradation 3-7h at 0-5 DEG C to 2-6；
(2) selenylation reaction: selenous acid or its salt are added in Xiang Shangshu carrageenan sol liquid, in an acidic solution through barium ions or calcium
It under ionic catalysis effect, is heated to reacting 8-14h at 30-80 DEG C, generates selenide of carragheen；
(3) remove barium or calcium ion: reaction solution is cooled to room temperature addition anhydrous sodium sulfate, make barium ions in reaction solution or calcium from
Son is generated as precipitating；Centrifugation removes precipitating；
(4) it neutralizes acid solution: the filtrate for removing precipitating in step (3) is adjusted into pH to 3-9 with lye；
(5) seperation film filters: the solution after step (4) are neutralized passes through nanofiltration membrane and ultrafiltration membrance filter respectively, removes unreacted
The inorganic substances such as selenite, small molecule selenide of carragheen and cross the selenide of carragheen of macromolecule, obtain molecular weight
The selenide of carragheen of 1000-10000；
(6) it is spray-dried: the every 100kg of filtrate in step (5) being added after 1-20kg maltodextrin is spray-dried and is made
Selenide of carragheen powder.
The preparation method of above-mentioned selenide of carragheen, it is characterised in that:
Ultrasonic power is 300-800W in the step (1).
The mass ratio of selenous acid or its salt and carragheen is 1:(1.5-15 in the step (2)).
Barium ions or calcium ion in the step (2) are BaCl2Or CaCl2One of.
Lye in the step (3) is one or more of NaOH, KOH or carbonate.
The molecular cut off of nanofiltration membrane is 1000 in the step (5).
The molecular cut off of ultrafiltration membrane is 10000 in the step (5).
Spray drying intake air temperature in the step (6) is 100-300 DEG C, and air outlet temperature is 20-200 DEG C.
It is relatively large for calcium sulfate solubility, to SO42-The bad problem of removal effect, flocculant can also be added
The concentration that adds of aluminium polychloride (PAC) and flocculation aid polyacrylamide (PAM), the PAC is 10-30mg/L, the PAM
Add concentration be 5-15mg/L.
The present invention has the advantage that
(1) ultrasonic degradation carragheen is used, compared with other methods, can simplify procedures, improve reaction rate and show
Write the waste the advantages that endangering caused by environment for reducing that chemical reaction generates, have the characteristics that more rapidly, mildly, it is environmentally friendly；
(2) it in carragheen degradation process, joined acetic acid, since carrageenan solutions are easier to hydrolyze in acidic environment, add
Enter to promote after acetic acid the degradation of carragheen；
(3) be filtered with seperation film, avoid and bring other elements substance into, more efficiently, science, it is environmentally protective will be organic
Macromolecular selenide of carragheen is separated with small molecule selenide of carragheen and other inorganic substances；
(4) mixed liquor is dried using spray drying device and powder is made, keep powder size more uniform, and be spray-dried
It is to be carried out in high-temperature closed space, there is high-temperature sterilization, production link is relatively sanitary, and product degree of purity is high；
(5) filtrate is spray-dried together with maltodextrin, final product characters powder obtained can not only be made more excellent
It is good, and the product of different size can more easily be made.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
In order to make the technological means of the invention realized it can be readily appreciated that with reference to the accompanying drawing and by specific embodiment to this hair
It is bright to be described further.
It is as shown in Figure 1 process flow chart of the invention.
Embodiment 1:
(1) degraded carrageenan: with deionized water by 1.0kg carragheen (Shanghai Bei Lian Biotechnology Co., Ltd, white uniformity powder
End) be made into mass concentration be 0.5% solution after, be added 5M acetum adjust solution ph reach 4.0, make solution in acidity,
Degradation reaction 7h is carried out using the ultrasonic wave that power is 300W under adjusting at 2 DEG C of ice bath；
(2) 0.16kg sodium selenite and 0.32kg BaCl selenylation reaction: are added into carrageenan sol liquid2, it is heated at 30 DEG C
14h is reacted, selenide of carragheen is generated；Reaction solution is down to room temperature by end of reaction；
(3) remove barium ions: 0.25kg anhydrous sodium sulfate is added in the reaction solution that room temperature is down to in step (2), makes in reaction solution
Barium ions be generated as precipitating；The reaction solution is centrifuged, barium sulfate precipitate is removed；
(4) it neutralizes acid solution: the filtrate for removing precipitating in step (3) is adjusted into pH to 6.5 with NaOH lye；
(5) seperation film filters: for 1000 nanofiltration membranes, (Beijing great Jing is easily logical by cutting molecular weight for the solution after step (4) are neutralized
Development in science and technology Co., Ltd, ULP31-4040) remove the selenizing card of the inorganic substances such as unreacted sodium selenite and small molecule
Glue is drawn, then the ultrafiltration membrane (Hangzhou Qing Sheng purification techniques Co., Ltd, QSUF-12) for being 10000 with molecular cut off removes big point
Son amount selenide of carragheen or unreacted carragheen obtain the selenide of carragheen crude product that weight average molecular weight is 1000-10000；
(6) refine: the crude product in step (5) is added after 3.0kg maltodextrin is spray-dried and selenide of carragheen powder is made
End, spray drying intake air temperature are 200 DEG C, and air outlet temperature is 100 DEG C, and Se content is in the finished product selenide of carragheen of preparation
2%。
Embodiment 2:
(1) degraded carrageenan: with deionized water by 1.5kg carragheen (Shanghai Bei Lian Biotechnology Co., Ltd, white uniformity powder
End) be made into mass concentration be 2% solution after, be added 5M acetum adjust solution ph reach 3.0, make solution in acidity,
5 DEG C of ice bath adjust the lower ultrasonic wave progress degradation reaction 5h using power for 500W；
(2) 0.68kg sodium selenite and 1.5kg BaCl selenylation reaction: are added into carrageenan sol liquid2, it is heated at 50 DEG C
10h is reacted, selenide of carragheen is generated；Reaction solution is down to room temperature by end of reaction；
(3) remove barium ions: 1.25kg anhydrous sodium sulfate is added in the reaction solution that room temperature is down to in step (2), makes in reaction solution
Barium ions be generated as precipitating；The reaction solution is centrifuged, barium sulfate precipitate is removed；
(4) it neutralizes acid solution: the filtrate for removing precipitating in step (3) is adjusted into pH to 7 with KOH lye；
(5) seperation film filters: the solution that step (4) are neutralized is 1000 nanofiltration membranes (Beijing great Jing Yi Tongke by cutting molecular weight
Skill Development Co., Ltd, ULP31-4040) remove the selenizing OK a karaoke club of the inorganic substances such as unreacted sodium selenite and small molecule
Glue, then the ultrafiltration membrane (Hangzhou Qing Sheng purification techniques Co., Ltd, QSUF-12) for being 10000 with molecular cut off remove macromolecular
Selenide of carragheen or unreacted carragheen are measured, the selenide of carragheen crude product that weight average molecular weight is 1000-10000 is obtained；
(6) it refines: selenide of carragheen is made by being added after 11.2kg maltodextrin is spray-dried in the crude product in step (5)
Powder, spray drying intake air temperature are 180 DEG C, and air outlet temperature is 100 DEG C, Se content in the finished product selenide of carragheen of preparation
It is 2.5%.
Embodiment 3:
(1) degraded carrageenan: with deionized water by 1.8kg carragheen (Shanghai Bei Lian Biotechnology Co., Ltd, white uniformity powder
End) be made into mass concentration be 2.5% solution after, be added 3M acetum adjust solution ph reach 3.5, make solution in acidity,
Degradation reaction 4.5h is carried out using the ultrasonic wave that power is 600W under adjusting at 3 DEG C of ice bath；
(2) 0.8kg sodium selenite and 1.75kg BaCl selenylation reaction: are added into carrageenan sol liquid2, it is heated at 70 DEG C
7h is reacted, selenide of carragheen is generated；Reaction solution is down to room temperature by end of reaction；
(3) remove barium ions: 1.56kg anhydrous sodium sulfate is added in the reaction solution that room temperature is down to in step (2), makes in reaction solution
Barium ions be generated as precipitating；The reaction solution is centrifuged, barium sulfate precipitate is removed；
(4) it neutralizes acid solution: the filtrate for removing precipitating in step (3) is adjusted into pH to 6 with KOH lye；
(5) seperation film filters: for 1000 nanofiltration membranes, (Beijing great Jing is easily logical by cutting molecular weight for the solution after step (4) are neutralized
Development in science and technology Co., Ltd, ULP31-4040) remove the selenizing card of the inorganic substances such as unreacted sodium selenite and small molecule
Glue is drawn, then the ultrafiltration membrane (Hangzhou Qing Sheng purification techniques Co., Ltd, QSUF-12) for being 10000 with molecular cut off removes big point
Son amount selenide of carragheen or unreacted carragheen obtain the selenide of carragheen crude product that weight average molecular weight is 1000-10000；
(6) it refines: the crude product in step (5) being added after 10kg maltodextrin is spray-dried, selenide of carragheen powder is made
End, spray drying intake air temperature are 210 DEG C, and air outlet temperature is 110 DEG C, and Se content is in the finished product selenide of carragheen of preparation
3%。
Embodiment 4:
(1) degraded carrageenan: with deionized water by 8.0kg carragheen (Shanghai Bei Lian Biotechnology Co., Ltd, white uniformity powder
End) be made into mass concentration be 1% solution after, be added 3M acetum adjust solution ph reach 3, make solution in acidity, in ice
It bathes 0 DEG C and adjusts the lower ultrasonic wave progress degradation reaction 3h using power for 800W；
(2) 0.8kg sodium selenite and 0.95kg CaCl selenylation reaction: are added into carrageenan sol liquid2, it is heated at 70 DEG C
7h is reacted, selenide of carragheen is generated；Reaction solution is down to room temperature by end of reaction；
(3) remove calcium ion: 1.28kg anhydrous sodium sulfate is added in the reaction solution that room temperature is down to in step (2), makes in reaction solution
Calcium ion be generated as precipitating；The PAM of the PAC and 10mg/L of 20mg/L, stir about 10 are separately added into above-mentioned reaction solution
Minute, it settles about 30 minutes；The reaction solution is centrifuged, calcium sulfate precipitation is removed；
(4) it neutralizes acid solution: the filtrate for removing precipitating in step step (3) is adjusted into pH to 6 with NaOH lye；
(5) seperation film filters: for 1000 nanofiltration membranes, (Beijing great Jing is easily logical by cutting molecular weight for the solution after step (4) are neutralized
Development in science and technology Co., Ltd, ULP31-4040) remove the selenizing card of the inorganic substances such as unreacted sodium selenite and small molecule
Glue is drawn, then the ultrafiltration membrane (Hangzhou Qing Sheng purification techniques Co., Ltd, QSUF-12) for being 10000 with molecular cut off removes big point
Son amount selenide of carragheen or unreacted carragheen obtain the selenide of carragheen crude product that weight average molecular weight is 1000-10000；
(6) it refines: by the crude product in step (5), being added after 9.6kg maltodextrin is spray-dried and selenide of carragheen powder is made
End, spray drying intake air temperature are 230 DEG C, and air outlet temperature is 120 DEG C, and the finished product selenide of carragheen Se content of preparation is
2%。
Finally, it should also be noted that it is enumerated above be only several specific embodiments of the invention.This field it is general
Logical technical staff will appreciate that, within the scope of the present invention, modify for above-described embodiment, and adding and replacing all is
Possible, all claimed without departing from present invention range.
Claims (9)
1. a kind of preparation method of selenide of carragheen, it is characterised in that the following steps are included:
(1) carragheen degrade: by carragheen be dissolved in water be made into mass concentration be 0.5%-4% solution after, be added acetic acid adjust it is molten
Liquid pH value controls temperature under ice-water bath and utilizes ultrasonic degradation 3-7h at 0-5 DEG C to 2-6；
(2) selenylation reaction: selenous acid or its salt are added in Xiang Shangshu carrageenan sol liquid, in an acidic solution through barium ions or calcium
It under ionic catalysis effect, is heated to reacting 8-14h at 30-80 DEG C, generates selenide of carragheen；
(3) remove barium or calcium ion: reaction solution is cooled to room temperature addition anhydrous sodium sulfate, make barium ions in reaction solution or calcium from
Son is generated as precipitating；Centrifugation removes precipitating；
(4) it neutralizes acid solution: the filtrate for removing precipitating in step (3) is adjusted into pH to 3-9 with lye；
(5) seperation film filters: the solution after step (4) are neutralized passes through nanofiltration membrane and ultrafiltration membrance filter respectively, removes unreacted
The inorganic substances such as selenite, small molecule selenide of carragheen and cross the selenide of carragheen of macromolecule, obtain molecular weight
The selenide of carragheen of 1000-10000；
(6) it is spray-dried: the every 100kg of filtrate in step (5) being added after 1-20kg maltodextrin is spray-dried and is made
Selenide of carragheen powder.
2. the preparation method of selenide of carragheen according to claim 1, it is characterised in that ultrasonic wave function in the step (1)
Rate is 300-800W.
3. the preparation method of selenide of carragheen according to claim 1, it is characterised in that in the step (2) selenous acid or
The mass ratio of its salt and carragheen is 1:(1.5-15).
4. the preparation method of selenide of carragheen according to claim 1, it is characterised in that the barium ions in the step (2)
Or calcium ion is BaCl2Or CaCl2One of.
5. the preparation method of selenide of carragheen according to claim 1, it is characterised in that the lye in the step (3) is
One or more of NaOH, KOH or carbonate.
6. the preparation method of selenide of carragheen according to claim 1, it is characterised in that in the step (3) before centrifugation
Further include the steps that adding flocculant poly aluminium chloride and flocculation aid polyacrylamide.
7. the preparation method of selenide of carragheen according to claim 1, it is characterised in that nanofiltration membrane in the step (5)
Molecular cut off is 1000.
8. the preparation method of selenide of carragheen according to claim 1, it is characterised in that ultrafiltration membrane in the step (5)
Molecular cut off is 10000.
9. the preparation method of selenide of carragheen according to claim 1, it is characterised in that spraying dry in the step (6)
Dry intake air temperature is 100-300 DEG C, and air outlet temperature is 20-200 DEG C.
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| CN112225915A (en) * | 2020-10-28 | 2021-01-15 | 青岛鹏洋生物工程有限公司 | Industrialized powder preparation process of selenocarrageenan |
| CN114391623A (en) * | 2021-12-31 | 2022-04-26 | 林欣 | Selenium-rich water functional beverage and preparation method thereof |
| WO2022151578A1 (en) * | 2021-01-15 | 2022-07-21 | 江苏大学 | Method for simultaneously improving flavor of soy sauce and increasing selenium content of soy sauce |
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