MD669Z - Process for producing alginates from brown algae - Google Patents
Process for producing alginates from brown algaeInfo
- Publication number
- MD669Z MD669Z MDS20130048A MDS20130048A MD669Z MD 669 Z MD669 Z MD 669Z MD S20130048 A MDS20130048 A MD S20130048A MD S20130048 A MDS20130048 A MD S20130048A MD 669 Z MD669 Z MD 669Z
- Authority
- MD
- Moldova
- Prior art keywords
- alginates
- algae
- solution
- citric acid
- acid
- Prior art date
Links
- 235000010443 alginic acid Nutrition 0.000 title claims abstract description 40
- 229920000615 alginic acid Polymers 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 16
- 241000199919 Phaeophyceae Species 0.000 title claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 241000195493 Cryptophyta Species 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 4
- 235000013305 food Nutrition 0.000 abstract description 4
- 238000013019 agitation Methods 0.000 abstract 1
- 239000012670 alkaline solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000000783 alginic acid Substances 0.000 description 16
- 229960001126 alginic acid Drugs 0.000 description 15
- 150000004781 alginic acids Chemical class 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 235000010413 sodium alginate Nutrition 0.000 description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 8
- 239000000661 sodium alginate Substances 0.000 description 8
- 229940005550 sodium alginate Drugs 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000010408 potassium alginate Nutrition 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000737 potassium alginate Substances 0.000 description 6
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 238000002803 maceration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 150000004804 polysaccharides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- AEMOLEFTQBMNLQ-SZXBDDMQSA-N (2s,3r,4r,5r,6s)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@@H](O)[C@H]1O AEMOLEFTQBMNLQ-SZXBDDMQSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000001364 causal effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 235000008504 concentrate Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 235000015071 dressings Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 235000013569 fruit product Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- ZYFXHKPHYKLIDV-UHFFFAOYSA-N hydrogen peroxide;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound OO.OC(=O)CC(O)(C(O)=O)CC(O)=O ZYFXHKPHYKLIDV-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Description
Invenţia se referă la industria alimentară şi poate fi utilizată pentru obţinerea alginaţilor din alge brune. The invention relates to the food industry and can be used to obtain alginates from brown algae.
Algele brune reprezintă surse naturale de polizaharide, în special de acid alginic. Macromoleculele acidului alginic sunt formate din resturi de acid β-D-manuronic şi acid α-D-guluronic, cu structură spaţială liniară. Distribuţia resturilor de acizi în structura lanţului macromoleculei are un caracter neuniform. Datorită acestei structuri alginaţii reprezintă fibre alimentare cu un spectru larg de aplicare practică. Acidul alginic este insolubil în apă. Sărurile acidului alginic, în special alginaţii de sodiu şi de potasiu, sunt solubile în apă, dar insolubile în alcooli. Alginaţii se consideră aditivi alimentari naturali, având codurile E 400…E 404, şi sunt admişi pentru utilizare în mai multe ţări, inclusiv în Republica Moldova. Alginaţii se utilizează în calitate de agenţi de îngroşare, de gelificare şi de stabilizare a texturii sosurilor, siropurilor, îngheţatei, berii, dresurilor, maionezei, sucurilor şi concentratelor, produselor lactate acide. De asemenea, alginaţii se utilizează la formarea peliculelor şi membranelor comestibile pe suprafaţa produselor din carne, peşte, fructe, pentru prevenirea modificărilor nedorite şi prelungirea termenului lor de valabilitate. Brown algae are natural sources of polysaccharides, especially alginic acid. The macromolecules of alginic acid are formed by residues of β-D-mannuronic acid and α-D-guluronic acid, with a linear spatial structure. The distribution of acid residues in the chain structure of the macromolecule is uneven. Due to this structure, alginates represent food fibers with a wide spectrum of practical application. Alginic acid is insoluble in water. Salts of alginic acid, especially sodium and potassium alginates, are soluble in water, but insoluble in alcohols. Alginates are considered natural food additives, having codes E 400...E 404, and are admitted for use in several countries, including the Republic of Moldova. Alginates are used as agents for thickening, gelling and stabilizing the texture of sauces, syrups, ice cream, beer, dressings, mayonnaise, juices and concentrates, acid dairy products. Also, alginates are used to form edible films and membranes on the surface of meat, fish, fruit products, to prevent unwanted changes and extend their shelf life.
Este cunoscut procedeul de prelucrare a algelor cu obţinerea produsului „Lamifarena” pe baza acidului alginic, conform căruia algele se mărunţesc până la dimensiuni de 3 mm, apoi se tratează cu soluţie de acid clorhidric (pH 6,0), timp de 5…6 ore, se tratează cu apă la temperatura de 20°C timp de 20 min, această operaţiune se repetă de 4 ori. Materia primă se tratează cu aburi timp de 16…20 ore, apoi se omogenizează mecanic până la obţinerea gelului alginic [1]. The process of processing algae to obtain the product "Lamifarena" based on alginic acid is known, according to which the algae are shredded up to 3 mm in size, then treated with hydrochloric acid solution (pH 6.0) for 5...6 hours, it is treated with water at a temperature of 20°C for 20 min, this operation is repeated 4 times. The raw material is treated with steam for 16...20 hours, then mechanically homogenized until the alginic gel is obtained [1].
Dezavantajul principal al acestui procedeu constă în tratarea termică îndelungată cu aburi a algelor, ceea ce duce la un consum excesiv de energie termică cu o posibilă reducere a masei moleculare a macromoleculelor acidului alginic. La spălarea de 4 ori a algelor mărunţite cu apă se pierde o parte din polizaharide cu masă moleculară inferioară datorită solubilizării lor la valorile pH-ului mai mari de 3,5 (M. Fukushima, K. Tatsumi, S. Wada. Evaluation of the Acid-Dissociation Constant of Alginic Acid. Analytical Sciences, 1999, V. 15, p.115-155). The main disadvantage of this process consists in the long thermal treatment of algae with steam, which leads to an excessive consumption of thermal energy with a possible reduction of the molecular mass of alginic acid macromolecules. When washing the crushed algae 4 times with water, a part of the lower molecular weight polysaccharides is lost due to their solubilization at pH values higher than 3.5 (M. Fukushima, K. Tatsumi, S. Wada. Evaluation of the Acid-Dissociation Constant of Alginic Acid. Analytical Sciences, 1999, V. 15, p.115-155).
Mai este cunoscut procedeul de prelucrare a algelor cu izolarea alginatului de sodiu, conform căruia algele se mărunţesc în particule cu dimensiuni de 5…15 mm, se tratează cu acizi timp de 0,5…1,5 ore la un pH de 2,0…4,0, se spală consecutiv cu apă marină şi apă dulce până la pH-ul de 6,0…6,6, apoi urmează tratarea cu bicarbonat de sodiu la temperatura de 60…70°C, timp de 10…15 min, omogenizarea şi congelarea [2]. The process of processing algae with the isolation of sodium alginate is also known, according to which the algae is crushed into particles with dimensions of 5...15 mm, treated with acids for 0.5...1.5 hours at a pH of 2.0 ...4.0, wash consecutively with sea water and fresh water until the pH is 6.0...6.6, then follow the treatment with sodium bicarbonate at a temperature of 60...70°C, for 10...15 min , homogenization and freezing [2].
Dezavantajul acestui procedeu constă în utilizarea acizilor minerali (HCl şi H2SO4) pentru spălarea preventivă a algelor şi a bicarbonatului de sodiu (NaHCO3) pentru hidroliza şi macerarea acestora. Prin urmare, se obţine o masă de acid alginic cu conţinut excesiv de anioni de Cl-, SO4 2-, HCO3 -. Procedeul nominalizat duce la coroziunea aparatajului şi la scăderea securităţii muncii, totodată nu asigură separarea alginaţilor în stare pură. The disadvantage of this process is the use of mineral acids (HCl and H2SO4) for preventive washing of algae and sodium bicarbonate (NaHCO3) for their hydrolysis and maceration. Therefore, a mass of alginic acid with an excessive content of Cl-, SO4 2-, HCO3 - anions is obtained. The nominated process leads to the corrosion of the apparatus and to the decrease of work safety, at the same time it does not ensure the separation of alginates in a pure state.
Unul din cele mai apropiate procedee de obţinere a acidului alginic şi alginatului de sodiu din alge brune prevede procesarea electrochimică a algelor cu soluţii de HCl şi NaOH, obţinute nemijlocit în spaţiul anodic şi catodic al celulelor electrolizorului. Purificarea alginatului de impurităţi solide se efectuează prin intermediul hidrogenului degajat în spaţiul catodic. Decolorarea extractului se realizează prin acţiunea hipocloritului, care se formează în spaţiul anodic. Separarea acidului alginic are loc prin electroliza extractului în spaţiul anodic până la pH-ul de 2,0 [3]. One of the closest processes for obtaining alginic acid and sodium alginate from brown algae involves the electrochemical processing of algae with HCl and NaOH solutions, obtained directly in the anodic and cathodic space of the electrolyzer cells. Purification of alginate from solid impurities is carried out by means of the hydrogen released in the cathode space. The discoloration of the extract is achieved by the action of hypochlorite, which is formed in the anodic space. The separation of alginic acid takes place by electrolysis of the extract in the anodic space up to a pH of 2.0 [3].
Dezavantajul acestui procedeu constă în aceea că nu se indică natura electrolitului utilizat la etapa separării acidului alginic, în acelaşi timp este cunoscut că la electroliza clorurii de sodiu în spaţiul anodic se descarcă ionul de clorură, deci formarea ionilor H+ este imposibilă. Probabil, în calitate de electrolit se utilizează sulfat de sodiu, electroliza căruia asigură formarea ionilor de hidrogen. Alt dezavantaj al acestui procedeu constă în utilizarea curentului electric. The disadvantage of this process is that the nature of the electrolyte used in the alginic acid separation stage is not indicated, at the same time it is known that during the electrolysis of sodium chloride in the anodic space the chloride ion is discharged, so the formation of H+ ions is impossible. Probably, sodium sulfate is used as an electrolyte, the electrolysis of which ensures the formation of hydrogen ions. Another disadvantage of this process is the use of electric current.
Problema pe care o rezolvă această invenţie constă în elaborarea unui procedeu nou de separare din alge brune a alginaţilor în stare solidă pură sub formă de fibre. The problem that this invention solves consists in the development of a new process for separating alginates from brown algae in a pure solid state in the form of fibers.
Procedeul, conform invenţiei, constă în aceea că algele se tratează cu soluţie de acid citric 0,1%, timp de 20…30 min, apoi într-un mediu alcalin cu un pH de 11,8…12,8, la temperatura de 65…70ºC, timp de 1…2 ore, fracţia lichidă se separă prin centrifugare, se tratează cu soluţie de peroxid de hidrogen de 30%, 2,0…3,0 ml/l şi acid citric 0,15…0,40 g/l, timp de 30 min, apoi se adaugă acid sulfuric concentrat la agitare continuă până la un pH de 2,0…3,0, gelul format se maturează timp de 30…45 min, se centrifughează, după care se adaugă o soluţie de o bază alcalină şi se filtrează prin cationit, alginaţii obţinuţi se precipită cu alcool etilic. The process, according to the invention, consists in treating the algae with a 0.1% citric acid solution for 20...30 min, then in an alkaline environment with a pH of 11.8...12.8, at a temperature of 65...70ºC, for 1...2 hours, the liquid fraction is separated by centrifugation, treated with 30% hydrogen peroxide solution, 2.0...3.0 ml/l and citric acid 0.15...0.40 g/l, for 30 min, then concentrated sulfuric acid is added with continuous stirring until a pH of 2.0...3.0, the gel formed matures for 30...45 min, it is centrifuged, after which a solution of an alkaline base and filter through cationite, the alginates obtained are precipitated with ethyl alcohol.
Legătura cauzală între elementele noi ale invenţiei şi rezultatul care poate fi obţinut prin realizarea invenţiei. The causal link between the new elements of the invention and the result that can be obtained by carrying out the invention.
Excluderea spălării cu apă măreşte randamentul alginaţilor. Spălarea cu apă provoacă înlăturarea cantităţilor importante de alginaţi solubili, datorită faptului că la conservarea şi uscarea algelor are loc distrugerea parţială a structurii lor celulare, care cauzează extracţia prematură a alginaţilor în urma spălării în medii apoase neutre, la valorile pH-ului de 5,0…9,0. Excluding water washing increases the yield of alginates. Washing with water causes the removal of important amounts of soluble alginates, due to the fact that during the preservation and drying of algae, their cellular structure is partially destroyed, which causes the premature extraction of alginates after washing in neutral aqueous environments, at pH values of 5, 0...9.0.
Utilizarea soluţiei acide cu pH < 3 la etapa spălării algelor diminuează considerabil pierderea alginaţilor. Acidul citric este un acid organic tribazic, cu masa moleculară echivalentă joasă (64 g/mol-echiv), de aceea el creează acidităţi relativ mari la concentraţii procentuale mici, asigurând coagularea bună a acidului alginic în interiorul şi la suprafaţa biomasei algelor la etapa spălării lor şi, respectiv, excluderea pierderilor alginaţilor sub formă de săruri solubile. Acidul citric este aprobat pentru utilizare ca adaos în industria alimentară, cosmetică şi farmaceutică. The use of the acid solution with pH < 3 at the stage of washing the algae considerably reduces the loss of alginates. Citric acid is a tribasic organic acid, with a low equivalent molecular mass (64 g/mol-equiv), therefore it creates relatively high acidity at low percentage concentrations, ensuring good coagulation of alginic acid inside and on the surface of the algae biomass at the washing stage and, respectively, the exclusion of alginate losses in the form of soluble salts. Citric acid is approved for use as an additive in the food, cosmetic and pharmaceutical industries.
Utilizarea bazelor alcaline tari, cu pH-ul 11,8…12,6, permite evitarea contaminării produselor finale cu exces de carbonaţi şi hidrogenocarbonaţi. La pH < 11,8 extracţia alginaţilor are loc cu un randament mic, iar la pH > 12,6 este posibilă hidroliza macromoleculelor şi, respectiv, scăderea randamentului alginaţilor polimerici cu masă moleculară mare. The use of strong alkaline bases, with a pH of 11.8...12.6, allows avoiding the contamination of the final products with excess carbonates and hydrogen carbonates. At pH < 11.8 the extraction of alginates takes place with a low yield, and at pH > 12.6 it is possible to hydrolyze macromolecules and, respectively, decrease the yield of high molecular weight polymeric alginates.
Utilizarea amestecului acid citric - apă oxigenată pentru decolorarea fazei lichide exclude contaminarea produsului finit cu ioni toxici de hipoclorit, care se folosesc în mod tradiţional pentru decolorare. Bule mici de oxigen, care se elimină la descompunerea H2O2, asigură afânarea gelului acidului alginic în timpul prelucrării fracţiei lichide cu acid sulfuric, contribuind la purificarea gelului. The use of the citric acid - hydrogen peroxide mixture for bleaching the liquid phase excludes contamination of the finished product with toxic hypochlorite ions, which are traditionally used for bleaching. Small bubbles of oxygen, which are eliminated during the decomposition of H2O2, ensure the loosening of the alginic acid gel during the processing of the liquid fraction with sulfuric acid, contributing to the purification of the gel.
Filtrarea prin cationit permite purificarea alginaţilor într-o singură etapă, evitând recristalizări multiple, costisitoare datorită utilizării volumelor mari de alcool sau de energie. Filtration through cationite allows the purification of alginates in a single step, avoiding multiple, expensive recrystallizations due to the use of large volumes of alcohol or energy.
Uscarea alginaţilor până la umiditatea relativă de 10…15% exclude necesitatea conservării chimice a produsului solid obţinut. Drying alginates to a relative humidity of 10...15% excludes the need for chemical preservation of the obtained solid product.
Exemplul 1 Example 1
Obţinerea alginatului de potasiu (KAlg) Obtaining potassium alginate (KAlg)
Algele brune uscate cu masa de 100 g se spală cu 3 l de soluţie care conţine 1 g/l de acid citric timp de 30 min. Masa alginică obţinută se decantează de soluţia acidă, apoi se acoperă cu 2 l soluţie de KOH cu pH-ul egal cu 12,6 şi se încălzeşte pe o baie de apă la temperatura de 70°C timp de 1 oră. Din maceratul obţinut se separă prin centrifugare 1,5 l de fracţie lichidă, care conţine alginat de potasiu, şi fracţia solidă, care conţine polizaharide, acizi organici, macro- şi microelemente. Fracţia lichidă se tratează cu 3 ml H2O2 - 30% şi 0,15 g de acid citric şi se lasă timp de 30 min. Apoi se adaugă acid sulfuric concentrat la agitare continuă, până la atingerea pH-ului de 3,0. Gelul format de acid alginic se lasă să se maturizeze timp de 30 min, apoi se centrifughează. Gelul solid obţinut se dizolvă în 50 ml soluţie, care conţine 4 g KOH. Soluţia obţinută de alginat de potasiu se filtrează prin 5 g de cationit. Alginatul de potasiu se precipită la adăugarea a 50 ml de alcool etilic. Masa solidă, rămasă după macerare, se aduce la pH-ul de 5,5 cu acid citric, se usucă până la umiditatea de 12%, obţinându-se fibre de culoare verzuie. Randamentul alginatului de potasiu în raport cu masa algelor uscate constituie 13,5%. Dry brown algae weighing 100 g are washed with 3 l of a solution containing 1 g/l of citric acid for 30 min. The obtained alginic mass is decanted from the acid solution, then covered with 2 l of KOH solution with a pH equal to 12.6 and heated on a water bath at a temperature of 70°C for 1 hour. From the obtained macerate, 1.5 l of the liquid fraction, which contains potassium alginate, and the solid fraction, which contains polysaccharides, organic acids, macro- and microelements, are separated by centrifugation. The liquid fraction is treated with 3 ml of H2O2 - 30% and 0.15 g of citric acid and left for 30 min. Concentrated sulfuric acid is then added with continuous stirring until a pH of 3.0 is reached. The gel formed by alginic acid is left to mature for 30 min, then centrifuged. The solid gel obtained is dissolved in 50 ml of solution containing 4 g of KOH. The obtained solution of potassium alginate is filtered through 5 g of cationite. Potassium alginate precipitates upon addition of 50 ml of ethyl alcohol. The solid mass, remaining after maceration, is brought to pH 5.5 with citric acid, dried to a humidity of 12%, obtaining greenish-colored fibers. The yield of potassium alginate in relation to the mass of dry algae is 13.5%.
Exemplul 2 Example 2
Extracţia repetată a alginatului de potasiu (KAlg) Repeated extraction of potassium alginate (KAlg)
Procedeul se efectuează conform exemplului 1 până la separarea maceratului în fracţie lichidă (1) şi fracţie solidă. Fracţia solidă se tratează cu 1,5 l soluţie de KOH cu pH-ul de 12,6, se omogenizează şi se încălzeşte până la 70°C. Amestecul obţinut se separă în fracţie lichidă (II) şi fracţie solidă. Fracţiile lichide (I) şi (II) se unesc, apoi fracţia lichidă unită şi fracţia solidă se prelucrează conform exemplului 1. Randamentul KAlg în raport cu masa algelor uscate constituie 15,0%. The procedure is carried out according to example 1 until the separation of the macerate into liquid fraction (1) and solid fraction. The solid fraction is treated with 1.5 l of KOH solution with a pH of 12.6, homogenized and heated to 70°C. The obtained mixture is separated into liquid fraction (II) and solid fraction. The liquid fractions (I) and (II) are combined, then the combined liquid fraction and the solid fraction are processed according to example 1. The KAlg yield in relation to the dry algae mass is 15.0%.
Exemplul 3 Example 3
Obţinerea alginatului de sodiu (NaAlg) Obtaining sodium alginate (NaAlg)
Algele brune uscate cu masa de 120 g se spală cu 3 l de soluţie, care conţine 1,2 g/l de acid citric timp de 20 min. Masa alginică obţinută se decantează, se acoperă cu 2,5 l soluţie de NaOH cu pH-ul de 12,8, apoi se încălzeşte la baia de apă la 65°C timp de 2 ore. Maceratul obţinut se centrifughează, din el se separă 2 l de fracţie lichidă, ce conţine alginat de sodiu. Fracţia lichidă se tratează cu 2 ml de H2O2 30% şi 0,4 g de acid citric şi se lasă timp de 30 min. Apoi se adaugă la agitare continuă acid sulfuric concentrat până la atingerea pH-ul de 2,0. Gelul format de acid alginic se lasă să se maturizeze timp de 45 min, apoi se centrifughează. Gelul solid obţinut se dizolvă în 50 ml de soluţie, care conţine 3 g NaOH. Soluţia obţinută de alginat de sodiu se filtrează prin 5 g de cationit. Alginatul de sodiu se precipită la adăugarea a 50 ml de alcool etilic. Masa solidă, rămasă după macerare, se aduce la pH-ul de 6,0 cu acid citric, se usucă până la umiditatea de 12% obţinându-se fibre de culoare galbenă-verzuie. Randamentul alginatului de sodiu în raport cu masa algelor uscate constituie 11,6%. Dry brown algae weighing 120 g are washed with 3 l of solution containing 1.2 g/l of citric acid for 20 min. The obtained alginic mass is decanted, covered with 2.5 l of NaOH solution with a pH of 12.8, then heated in a water bath at 65°C for 2 hours. The obtained macerate is centrifuged, 2 liters of liquid fraction containing sodium alginate are separated from it. The liquid fraction is treated with 2 ml of H2O2 30% and 0.4 g of citric acid and left for 30 min. Concentrated sulfuric acid is then added with continuous stirring until a pH of 2.0 is reached. The gel formed by alginic acid is left to mature for 45 min, then centrifuged. The solid gel obtained is dissolved in 50 ml of solution containing 3 g of NaOH. The sodium alginate solution obtained is filtered through 5 g of cationite. Sodium alginate precipitates upon addition of 50 ml of ethyl alcohol. The solid mass, remaining after maceration, is brought to pH 6.0 with citric acid, dried to a humidity of 12%, obtaining greenish-yellow fibers. The yield of sodium alginate in relation to the mass of dry algae is 11.6%.
Exemplul 4 Example 4
Extracţia repetată a alginatului de sodiu (NaAlg) Repeated extraction of sodium alginate (NaAlg)
Procedeul se efectuează la fel ca în exemplul 3 până la separarea maceratului în fracţie lichidă (I) şi fracţie solidă. Fracţia solidă se tratează cu 2 l de soluţie NaOH cu pH-ul de 12,4, se omogenizează şi se încălzeşte până la 70°C. Amestecul obţinut se separă în fracţie lichidă (II) şi fracţie solidă. Fracţiile lichide (I) şi (II) se unesc, apoi fracţia lichidă unită şi fracţia solidă se prelucrează conform exemplului 3. Randamentul NaAlg constituie 12,9%. The procedure is carried out in the same way as in example 3 until the separation of the macerate into liquid fraction (I) and solid fraction. The solid fraction is treated with 2 l of NaOH solution with a pH of 12.4, homogenized and heated to 70°C. The obtained mixture is separated into liquid fraction (II) and solid fraction. The liquid fractions (I) and (II) are combined, then the combined liquid fraction and the solid fraction are processed according to example 3. The yield of NaAlg is 12.9%.
Tabel Table
Compararea eficienţei exemplelor, referitoare la realizarea invenţiei Comparison of the efficiency of the examples, related to the realization of the invention
Consum acid citric, g Consum bază, g Consum H2O2, ml Consum acid sulfuric, ml Randament MeAlg, % Exemplul 1 3,4 6,7 3,0 1,0 13,5 Exemplul 2 3,6 10,0 4,5 2,0 15,0 Exemplul 3 4,4 3,0 4,0 3,0 11,6 Exemplul 4 4,8 4,5 6,0 6,0 12,9 Citric acid consumption, g Base consumption, g H2O2 consumption, ml Sulfuric acid consumption, ml MeAlg yield, % Example 1 3.4 6.7 3.0 1.0 13.5 Example 2 3.6 10.0 4.5 2.0 15.0 Example 3 4.4 3.0 4.0 3.0 11.6 Example 4 4.8 4.5 6.0 6.0 12.9
Datele din tabel demonstrează că extracţia repetată a alginaţilor măreşte randamentul lor. Însă are şi dezavantaje: se măreşte numărul de operaţiuni şi consumul de reactivi. De aceea realizarea procedeului conform exemplului 1 şi 2 este mai raţională. The data in the table demonstrate that repeated extraction of alginates increases their yield. But it also has disadvantages: the number of operations and the consumption of reagents increases. That is why carrying out the procedure according to example 1 and 2 is more rational.
1. RU 2230464 C1 2004.06.20 1. RU 2230464 C1 2004.06.20
2. RU 2019981 C1 1994.09.30 2. RU 2019981 C1 1994.09.30
3. RU 2001105012 A 2003.01.20 3. RU 2001105012 A 2003.01.20
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1351565A1 (en) * | 1985-06-06 | 1987-11-15 | Тихоокеанский научно-исследовательский институт рыбного хозяйства и океанографии | Method of producing salts of alginic acid |
| SU1450810A1 (en) * | 1986-10-16 | 1989-01-15 | Ленинградская лесотехническая академия им.С.М.Кирова | Method of producing sodium alginate from sea staff |
| SU1703035A1 (en) * | 1989-10-03 | 1992-01-07 | Научно-исследовательский институт химии Саратовского государственного университета им.Н.Г.Чернышевского | Method of obtaining calcium alginate |
| RU2019981C1 (en) * | 1991-06-25 | 1994-09-30 | Маслюков Юрий Павлович | Method for processing algae into product containing sodium alginate |
| RU2030885C1 (en) * | 1991-06-25 | 1995-03-20 | Маслюков Юрий Павлович | Algae reprocessing method for obtaining product containing calcium alginate |
| RU2041656C1 (en) * | 1991-10-23 | 1995-08-20 | Тихоокеанский научно-исследовательский институт рыбного хозяйства и океанографии | Method for manufacture of nutritional semi-finished product from laminaria algae |
| RU2142812C1 (en) * | 1998-04-21 | 1999-12-20 | Товарищество с ограниченной ответственностью "Научно-производственная фирма "Фаркос" | Method for complex processing of dry seaweed raw materials |
| RU2001105012A (en) * | 2001-02-21 | 2003-01-20 | Государственное унитарное предприятие "Государственный научно-исследовательский и проектно-конструкторский институт по развитию и эксплуатации флота "ГИПРОРЫБФЛОТ" | METHOD FOR PRODUCING ALGINIC ACID AND SODIUM ALGINATE FROM BROWN ALGAE |
| RU2197840C2 (en) * | 2001-02-21 | 2003-02-10 | Государственное унитарное предприятие "Государственный научно-исследовательский и проектно-конструкторский институт по развитию и эксплуатации флота "ГИПРОРЫБФЛОТ" | Method of preparing alginic acid and sodium alginate from brown algae |
| RU2204395C1 (en) * | 2002-09-16 | 2003-05-20 | Федеральное государственное унитарное предприятие Тихоокеанский научно-исследовательский рыбохозяйственный центр ФГУП "ТИНРО-Центр" | Method for preparing alginic acid complex salt |
| RU2230464C1 (en) * | 2002-10-09 | 2004-06-20 | Кудрявцев Олег Николаевич | Method for processing algae for preparing product "lamifaren" |
| RU2233104C1 (en) * | 2002-12-09 | 2004-07-27 | Федеральное государственное унитарное предприятие Тихоокеанский научно-исследовательский рыбохозяйственный центр ФГУП "ТИНРО-Центр" | Method for complex reprocessing of brown algae for producing of iodine-containing and polysaccharide products |
| RU2240816C1 (en) * | 2003-07-28 | 2004-11-27 | Тихоокеанский институт биоорганической химии Дальневосточного отделения РАН | Method for complex processing brown algae for preparing preparations for medicine and cosmetology |
| RU2007117702A (en) * | 2004-10-12 | 2008-11-20 | ФМС БиоПолимер АС (NO) | SELF-GELINING ALGINATE SYSTEMS AND THEIR APPLICATION |
| RU2008143160A (en) * | 2008-10-30 | 2010-05-10 | Институт биологии моря им. А.В. Жирмунского Дальневосточного отделения Российской академии наук (RU) | METHOD FOR PRODUCING CALCIUM ALGINATE |
| RU2399298C1 (en) * | 2009-05-21 | 2010-09-20 | Тихоокеанский Институт Биоорганической Химии Дальневосточного Отделения Российской Академии Наук (Тибох Дво Ран) | Method of processing brown algae |
| RU2009121678A (en) * | 2009-06-08 | 2010-12-20 | Алексей Глебович Одинец (RU) | METHOD FOR PRODUCING BIOLOGICALLY ACTIVE PRODUCTS FROM BROWN ALGAE AND FRUIT |
-
2013
- 2013-03-14 MD MDS20130048A patent/MD669Z/en not_active IP Right Cessation
Patent Citations (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1351565A1 (en) * | 1985-06-06 | 1987-11-15 | Тихоокеанский научно-исследовательский институт рыбного хозяйства и океанографии | Method of producing salts of alginic acid |
| SU1450810A1 (en) * | 1986-10-16 | 1989-01-15 | Ленинградская лесотехническая академия им.С.М.Кирова | Method of producing sodium alginate from sea staff |
| SU1703035A1 (en) * | 1989-10-03 | 1992-01-07 | Научно-исследовательский институт химии Саратовского государственного университета им.Н.Г.Чернышевского | Method of obtaining calcium alginate |
| RU2019981C1 (en) * | 1991-06-25 | 1994-09-30 | Маслюков Юрий Павлович | Method for processing algae into product containing sodium alginate |
| RU2030885C1 (en) * | 1991-06-25 | 1995-03-20 | Маслюков Юрий Павлович | Algae reprocessing method for obtaining product containing calcium alginate |
| RU2041656C1 (en) * | 1991-10-23 | 1995-08-20 | Тихоокеанский научно-исследовательский институт рыбного хозяйства и океанографии | Method for manufacture of nutritional semi-finished product from laminaria algae |
| RU2142812C1 (en) * | 1998-04-21 | 1999-12-20 | Товарищество с ограниченной ответственностью "Научно-производственная фирма "Фаркос" | Method for complex processing of dry seaweed raw materials |
| RU2197840C2 (en) * | 2001-02-21 | 2003-02-10 | Государственное унитарное предприятие "Государственный научно-исследовательский и проектно-конструкторский институт по развитию и эксплуатации флота "ГИПРОРЫБФЛОТ" | Method of preparing alginic acid and sodium alginate from brown algae |
| RU2001105012A (en) * | 2001-02-21 | 2003-01-20 | Государственное унитарное предприятие "Государственный научно-исследовательский и проектно-конструкторский институт по развитию и эксплуатации флота "ГИПРОРЫБФЛОТ" | METHOD FOR PRODUCING ALGINIC ACID AND SODIUM ALGINATE FROM BROWN ALGAE |
| RU2204395C1 (en) * | 2002-09-16 | 2003-05-20 | Федеральное государственное унитарное предприятие Тихоокеанский научно-исследовательский рыбохозяйственный центр ФГУП "ТИНРО-Центр" | Method for preparing alginic acid complex salt |
| RU2230464C1 (en) * | 2002-10-09 | 2004-06-20 | Кудрявцев Олег Николаевич | Method for processing algae for preparing product "lamifaren" |
| RU2002133172A (en) * | 2002-12-09 | 2004-06-10 | Федеральное государственное унитарное предприятие Тихоокеанский научно-исследовательский рыбохозяйственный центр | METHOD FOR COMPLEX PROCESSING OF BROWN ALGAE WITH PRODUCTION OF IODINE-CONTAINING AND POLYSACCHARIDE PRODUCTS |
| RU2233104C1 (en) * | 2002-12-09 | 2004-07-27 | Федеральное государственное унитарное предприятие Тихоокеанский научно-исследовательский рыбохозяйственный центр ФГУП "ТИНРО-Центр" | Method for complex reprocessing of brown algae for producing of iodine-containing and polysaccharide products |
| RU2240816C1 (en) * | 2003-07-28 | 2004-11-27 | Тихоокеанский институт биоорганической химии Дальневосточного отделения РАН | Method for complex processing brown algae for preparing preparations for medicine and cosmetology |
| RU2007117702A (en) * | 2004-10-12 | 2008-11-20 | ФМС БиоПолимер АС (NO) | SELF-GELINING ALGINATE SYSTEMS AND THEIR APPLICATION |
| RU2008143160A (en) * | 2008-10-30 | 2010-05-10 | Институт биологии моря им. А.В. Жирмунского Дальневосточного отделения Российской академии наук (RU) | METHOD FOR PRODUCING CALCIUM ALGINATE |
| RU2395525C1 (en) * | 2008-10-30 | 2010-07-27 | Институт биологии моря им. А.В. Жирмунского Дальневосточного отделения Российской академии наук | Method of producing calcium alginate |
| RU2399298C1 (en) * | 2009-05-21 | 2010-09-20 | Тихоокеанский Институт Биоорганической Химии Дальневосточного Отделения Российской Академии Наук (Тибох Дво Ран) | Method of processing brown algae |
| RU2009121678A (en) * | 2009-06-08 | 2010-12-20 | Алексей Глебович Одинец (RU) | METHOD FOR PRODUCING BIOLOGICALLY ACTIVE PRODUCTS FROM BROWN ALGAE AND FRUIT |
Non-Patent Citations (2)
| Title |
|---|
| <http://facultate.regielive.ro/proiecte/chimie-generala/alginatul-de-sodiu-agronomie-127456.html> * |
| <http://www.revistadechimie.ro/pdf/PER..pdf> * |
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