CN104341537A - Method for arsenic removal and extraction of nutrient substances in sargassum fusiforme - Google Patents
Method for arsenic removal and extraction of nutrient substances in sargassum fusiforme Download PDFInfo
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- CN104341537A CN104341537A CN201310341402.3A CN201310341402A CN104341537A CN 104341537 A CN104341537 A CN 104341537A CN 201310341402 A CN201310341402 A CN 201310341402A CN 104341537 A CN104341537 A CN 104341537A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
The invention discloses a method for arsenic removal and extraction of nutrient substances in sargassum fusiforme, and is characterized in that the method comprises the following steps: (1) arsenic removal treatment, (2) cellulose enzymolysis, (3) proteolysis, (4) brine digestion, (5) dilution and filtration, (6) decoloring, (7) CaCl2 solution treatment, (8) ion exchange, (9) preparation of sodium alginate, (10) preparation of ethanol, and (11) preparation of a seaweed organic fertilizer. The sargassum fusiforme arsenic removal process provided by the invention greatly reduces the arsenic content in sargassum fusiforme, then a composite enzyme is prepared from protease, pectinase and cellulase by a scientific ratio, and raw material is pretreated, so as to improve the extraction rate of sodium alginate; at the same time, fuel ethanol is prepared by using cellulose-rich sargassum fusiforme processing waste; waste liquid and waste residues remaining in the processing process are used for manufacturing the seaweed organic fertilizer through concentration, spray drying and granulation, so as to realize the high-valued comprehensive utilization of sargassum fusiforme.
Description
Technical field
The present invention relates to Sargassum fusiforme and utilize field, be specifically related to a kind of method that Sargassum fusiforme Middle nutrition material is extracted in dearsenification.
Background technology
Our times is faced with the immense pressure of energy shortage and environmental pollution, and the renewable energy source that exploitation is cleaned has become the important means solving fossil resources and energy dilemma.Bio-ethanol is subject to extensive concern as a kind of clean fuel and gasoline dope.At present, China prepares alcohol fuel and mainly lays particular emphasis on the Lu Yuan raw materials such as stalk, bagasse, wood chip and cassava, but it is less to prepare the research of bio-ethanol to Living marine resources, the backwardness relatively of the technical study in seaweed biomass energy development.
Ocean area is huge, and be richly stored with marine algae resource, and it is of a great variety, photosynthetic efficiency is high, growth cycle is short, and the biomass total amount produced by photosynthesis every year just reaches 550x10
8ton is a kind of huge renewable resources, is also the potential resources producing biomass energy.In Sargassum fusiforme Industrial processes, produce a large amount of Sargassum fusiforme trade wastes, the main component of these trade wastes is Mierocrystalline cellulose, Hijiki polysaccharide, N.F,USP MANNITOL etc.; The wherein Mierocrystalline cellulose monose and oligosaccharides that different modes can be utilized to be converted into can be utilized, N.F,USP MANNITOL and most of Sargassum polysaccharides class material can be all ethanol through microbe conversion.The Sargassum fusiforme processing waste of rich cellulose, Hijiki polysaccharide, N.F,USP MANNITOL is utilized to prepare alcohol fuel, Sargassum fusiforme processing waste not only can be made to turn waste into wealth, solve problem of environmental pollution, also can be the raw material supply prepared bio-ethanol and provide sufficient and cheap, promote the technological development of the marine biomass energy.
Sargassum fusiforme, a kind of phycophyta, frond tawny, plump succulence, thallophytic variation is very large, and shape is various.Growth, on low tide band rock, is distributed in China coast more.Medically there is effect of dietotherapy.
Sargassum fusiforme, to prevention thyromegaly, reduces in blood and takes sterol, and treatment hypertension and large bowel cancer, cancer of the stomach, all have certain effect; And to the growth of promotion bone in children road, keep skin lubrication, recover brain fag, prevent aging etc., also have the effect shown.Algae has the effect of arsenic in enriching seawater usually, and Sargassum fusiforme is natural in a large amount of arsenic, the inorganic arsenic that especially toxicity is higher.Arsenic is natural is present in the earth's crust, and stone, earth, water and air have the arsenic of trace.In food, arsenic can exist with organic and inorganic forms.Human consumption to the approach of arsenic, mainly through feed food, the aquatic food that particularly arsenic content is higher.Scientific evidence shows, even if the arsenic absorbed only has several grams, also can cause acute or subacute poisoning.In general, the toxicity of inorganic arsenic is high compared with organoarsenic.The gi tract meeting severe inflammation of acute poisoning person, thus causes vomiting and diarrhoea, more seriously can cause the multiple organ failure of health.Other symptoms comprise fever, become thin, easily irritability, epilation etc.Subordinate's international cancer research organization of the World Health Organization has been classified as arsenic can make us cancered material.
Sodium alginate, a kind of natural polysaccharide, has the stability needed for pharmaceutical preparation auxiliary material, solvability, viscosity and security.1881, first Englishize scholar E.C.Stanford carried out scientific research to the alginates extract in brown seaweed.He finds that this alignic extract has several very interesting characteristic, and it has concentrated solution, forms the ability of gel and film forming.Based on this, he proposes the application of several suitability for industrialized production.But alginates is until 50 years just carry out large-scale industrial production.Commercially produce and start from nineteen twenty-seven, the present whole world about produces 30000 tons every year, and wherein 30% for foodstuffs industry, and remaining is industrial for other, pharmacy industry and dentistry.
Current zymohydrolysis extracting method sodium alginate extraction is ripe not enough, often all just have employed single cellulase to be hydrolyzed, but composition plant cell wall has the compositions such as cellulase, hemicellulase, pectin, xylogen, on-link mode (OLM) between them or inlay, or obvolvent, so be difficult to single enzyme the cell walls thoroughly cracking plant, content can not be made to discharge completely.
How on the basis of sargassum fusiforme dearsenifying, thoroughly crack the cell walls of plant, content is discharged completely.Avoid again being subject to other people's molecular substance, as the interference of pectin, protein etc., the present invention considers to make prozyme with proteolytic enzyme, polygalacturonase, cellulase by the proportioning of science, pre-treatment is carried out to raw material, and then on the basis of sodium alginate extraction, make full use of Sargassum fusiforme and produce ethanol and seaweed organic fertilizer.
Summary of the invention
For solving the technical barrier existed in above-mentioned technology, the object of this invention is to provide a kind of method that Sargassum fusiforme Middle nutrition material is extracted in dearsenification, achieve yield and the viscosity thereof of sodium alginate extraction from dearsenification Sargassum fusiforme, reduce the consumption of pharmaceutical chemicals, be that a kind of exploitation and Sargassum fusiforme of ethanol cleans, the novel method of high-valued, comprehensive utilization.
For achieving the above object, the invention provides a kind of method that Sargassum fusiforme Middle nutrition material is extracted in dearsenification, it is characterized in that, described method comprises the steps:
(1) dearsenification process: Sargassum fusiforme 50-55 DEG C warm water is cleaned three times, is broken for the segment of 20-50mm, then puts in enzymolysis pot, adds 10-20 times of water, the EDTA of 0.5-1%, is warmed up to 50-60 DEG C and keeps 40-50 minute;
(2) fiber enzymolysis: and adjust liquid pH value to 3-6 with HCl, add the cellulase 0.4-0.6% be made up of inscribe β-dextranase 50%, circumscribed β-dextranase 25%, β-glucose lucerne enzyme 25%, enzymolysis 7-10h;
(3) proteolysis: add the proteinase-10 .3-0.5% be made up of neutral protease 40%, papoid 60%, the polygalacturonase 0.3-0.5% be made up of pectin lyase 50%, Rohapect MPE 50%, continues enzymolysis 2-4h, stirs, centrifugation after enzymolysis;
(4) salt solution digestion: to above-mentioned centrifugal after Sargassum fusiforme in add the 2-3% Na of 10-12 times of Sargassum fusiforme weight
2cO
3solution, digests 2-3h in 55-65 DEG C of water-bath;
(5) dilute filtration: the fresh tap water then adding volume 5-7 times 50-60 DEG C carries out dilution 1-2h, fully after dilution evenly, is filtered by 280-350 object tulle;
(6) decolour: filtrate adds the hydrogen peroxide of 0.2-0.3%, at 50-60 DEG C of decolouring 1-2h, be then warmed up to 80-90 DEG C and keep 10-20min, filter with 280-350 object tulle;
(7) CaCl
2solution-treated: filtrate slowly adds the CaCl of volume ratio 2-3% concentration 10%
2solution, leaves standstill 1-2h, then filters, with CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity;
(8) ion-exchange: calcium alginate adds 12-15 purified water doubly, then by 1-2 doubly 10% NaCl solution, carries out ion-exchange, makes calcium alginate fiber be converted into sodium alginate solution completely in 50 DEG C of water-baths;
(9) sodium alginate processed: then use the alcohol precipitation of 95%, obtains sodium alginate, and sodium alginate obtains finished product through dehydration, oven dry, pulverizing;
(10) ethanol processed: the centrifugal filtrate autoclaving in step (3), after cooling, adds activated yeast, and inoculative proportion is 15-20%, 27-35 DEG C and seals and continue to cultivate fermentation in 4-8 days, and ethanol is produced in fermented liquid distillation;
(11) seaweed organic fertilizer processed: contain a large amount of compositions such as protein, nitrogen, phosphorus, potassium, the liquid after ethanol evaporation in remaining liquid after distillation ethanol, after being concentrated to 45-60% concentration, spray is dry, granulation, prepares seaweed organic fertilizer.
The method of Sargassum fusiforme Middle nutrition material is extracted in above-mentioned a kind of dearsenification, it is characterized in that: fermentative production of ethanol in described step (10), after enzymolysis solution sterilizing, accesses activated industrial yeast bacterial classification CICC31447, carries out fermentation culture.
The method of Sargassum fusiforme Middle nutrition material is extracted in above-mentioned a kind of dearsenification, it is characterized in that: described step (10) fermentative production of ethanol, and enzymolysis solution is through the yeast of overactivation at 30 DEG C, and fermentation culture 7 days, the bio-ethanol amount obtained is maximum.
Beneficial effect of the present invention:
Sargassum fusiforme dearsenifying process provided by the invention greatly reduces the arsenic content in Sargassum fusiforme, methodological science, simple, safe and effective, is convenient to industrialization operate continuously, does not introduce new pollutent, do not produce new dangerous material.For the safe edible of Sargassum fusiforme and the exploitation of following related products provide safety assurance.The present invention makes prozyme with proteolytic enzyme, polygalacturonase, cellulase by the proportioning of science, avoid being subject to other people's molecular substance, as the interference of pectin, protein etc., pre-treatment is carried out to raw material, thoroughly crack the cell walls of plant, the main components such as the Mierocrystalline cellulose in Sargassum fusiforme, protein are separated, and is converted into the available monose of microorganism, oligosaccharides and free protein, be conducive to the extraction yield improving sodium alginate; Utilize the Sargassum fusiforme processing waste of rich cellulose to prepare alcohol fuel simultaneously; Remaining waste liquid and waste residue in the course of processing, by concentrating, spraying dry, granulation manufacture seaweed organic fertilizer, achieve the high-valued comprehensive utilization of Sargassum fusiforme, develop the marine organisms energy.
Embodiment
embodiment 1:
Sargassum fusiforme 50-55 DEG C warm water is cleaned three times, is broken for the segment of 20-50mm, amount to 100g and put in enzymolysis pot, add 1000g water, the EDTA of 0.5%, be warmed up to 50 DEG C and keep 40 minutes; Then HCl adjust ph to 3 is used, add the cellulase 0.4% be made up of inscribe β-dextranase 50%, circumscribed β-dextranase 25%, β-glucose lucerne enzyme 25%, enzymolysis 7h, add the proteinase-10 .3% be made up of neutral protease 40%, papoid 60%, the polygalacturonase 0.3% be made up of pectin lyase 50%, Rohapect MPE 50%, continue enzymolysis 2h, enzymolysis process constantly stirs, enzymolysis terminates rear centrifugation, obtains pretreated Sargassum fusiforme and enzymolysis solution.
Pretreated Sargassum fusiforme adds the 2%Na of 1000ml
2cO
3solution, 2h is digested in 55 DEG C of water-baths, then the fresh tap water adding 50 DEG C of volume 5000ml carries out dilution 1h, after abundant dilution evenly, filtered by 280 object tulles, filtrate adds the hydrogen peroxide of 5ml, at 50 DEG C of decolouring 1h, then be warmed up to 80 DEG C and keep 10min, filter with 280 object tulles, filtrate slowly adds the CaCl of 60ml concentration 10%
2solution, is converted into calcium alginate and separates out, leave standstill 1h, then filter by sodium alginate wherein, with CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity; Calcium alginate adds 2400ml purified water, then 10% NaCl solution of 1000ml is used, ion-exchange is carried out in 50 DEG C of water-baths, calcium alginate fiber is made to be converted into sodium alginate solution completely, then the alcohol precipitation of 95% is used, obtain sodium alginate, sodium alginate obtains finished product 23.5 grams through dehydration, oven dry, pulverizing.
First industrial yeast is placed in nutrient solution and cultivates activation, medium component is 1% yeast extract paste, 2% peptone, 2% glucose, above raw material is dissolved in water, in 121 DEG C of sterilizing 15min, then inoculate in clean operator's console, cultivate 1 day, by pretreated for Sargassum fusiforme enzymolysis solution autoclaving, after cooling for 30 DEG C, add activated yeast, inoculative proportion is 10%, 28 DEG C and seals and continue cultivation fermentation in 3 days, and ethanol is produced in fermented liquid distillation, after cultivation terminates, the alcohol concn measured wherein is about 3.2%, after distillation, obtains bio-ethanol.Contain a large amount of compositions such as protein, nitrogen, phosphorus, potassium in remaining liquid after distillation ethanol, the liquid after ethanol evaporation is by the concentrated raw material as producing seaweed organic fertilizer
Bio-ethanol fermented distilled go out after ethanol, it is 50% that remaining fermentation raffinate is concentrated to concentration, and then spray is dry, and pulverize, make seaweed organic fertilizer, the content of the N P and K in fertilizer is about 12%, and the content of total organic matter is 41%.
embodiment 2:
Sargassum fusiforme about 55 DEG C warm water are cleaned three times, is broken for the segment of 50mm, amount to 100g and then put in enzymolysis pot, add 2000g water, the EDTA of 1%, be warmed up to about 60 DEG C and keep 50 minutes; Then HCl adjust ph to 6 is used, add the cellulase 0.6% be made up of inscribe β-dextranase 50%, circumscribed β-dextranase 25%, β-glucose lucerne enzyme 25%, enzymolysis 10h, add the proteinase-10 .5% be made up of neutral protease 40%, papoid 60%, the polygalacturonase 0.5% be made up of pectin lyase 50%, Rohapect MPE 50%, continue enzymolysis 4h, enzymolysis process constantly stirs, enzymolysis terminates rear centrifugation, obtains pretreated Sargassum fusiforme and enzymolysis solution.
Pretreated Sargassum fusiforme adds the 3%Na of 1200ml
2cO
3solution, 3h is digested in 65 DEG C of water-baths, then the fresh tap water adding 60 DEG C of volume 7000ml carries out dilution 2h, after abundant dilution evenly, filtered by 350 object tulles, filtrate adds the hydrogen peroxide of 7ml, at 60 DEG C of decolouring 2h, then be warmed up to 90 DEG C and keep 20min, filter with 350 object tulles, filtrate slowly adds the CaCl of 90ml concentration 10%
2solution, is converted into calcium alginate and separates out, leave standstill 2h, then filter by sodium alginate wherein, with CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity; Calcium alginate adds 3000ml purified water, then 10% NaCl solution of 2000ml is used, ion-exchange is carried out in 50 DEG C of water-baths, calcium alginate fiber is made to be converted into sodium alginate solution completely, then the alcohol precipitation of 95% is used, obtain sodium alginate, sodium alginate obtains finished product 26.3 grams through dehydration, oven dry, pulverizing.
First industrial yeast is placed in nutrient solution and cultivates activation, medium component is 1% yeast extract paste, 2% peptone, 2% glucose, above raw material is dissolved in water, in 121 DEG C of sterilizing 15min, then inoculate in clean operator's console, cultivate 1 day, by pretreated for Sargassum fusiforme enzymolysis solution autoclaving, after cooling for 30 DEG C, add activated yeast, inoculative proportion is 10%, 28 DEG C and seals and continue cultivation fermentation in 3 days, and ethanol is produced in fermented liquid distillation, after cultivation terminates, the alcohol concn measured wherein is about 3.2%, after distillation, obtains bio-ethanol.Contain a large amount of compositions such as protein, nitrogen, phosphorus, potassium in remaining liquid after distillation ethanol, the liquid after ethanol evaporation is by the concentrated raw material as producing seaweed organic fertilizer
Bio-ethanol fermented distilled go out after ethanol, it is 50% that remaining fermentation raffinate is concentrated to concentration, and then spray is dry, and pulverize, make seaweed organic fertilizer, the content of the N P and K in fertilizer is about 12%, and the content of total organic matter is 48%.
Claims (3)
1. a method for Sargassum fusiforme Middle nutrition material is extracted in dearsenification, and it is characterized in that, described method comprises the steps:
(1) dearsenification process: Sargassum fusiforme 50-55 DEG C warm water is cleaned three times, is broken for the segment of 20-50mm, then puts in enzymolysis pot, adds 10-20 times of water, the EDTA of 0.5-1%, is warmed up to 50-60 DEG C and keeps 40-50 minute;
(2) fiber enzymolysis: and adjust liquid pH value to 3-6 with HCl, add the cellulase 0.4-0.6% be made up of inscribe β-dextranase 50%, circumscribed β-dextranase 25%, β-glucose lucerne enzyme 25%, enzymolysis 7-10h;
(3) proteolysis: add the proteinase-10 .3-0.5% be made up of neutral protease 40%, papoid 60%, the polygalacturonase 0.3-0.5% be made up of pectin lyase 50%, Rohapect MPE 50%, continues enzymolysis 2-4h, stirs, centrifugation after enzymolysis;
(4) salt solution digestion: to above-mentioned centrifugal after Sargassum fusiforme in add the 2-3% Na of 10-12 times of Sargassum fusiforme weight
2cO
3solution, digests 2-3h in 55-65 DEG C of water-bath;
(5) dilute filtration: the fresh tap water then adding volume 5-7 times 50-60 DEG C carries out dilution 1-2h, fully after dilution evenly, is filtered by 280-350 object tulle;
(6) decolour: filtrate adds the hydrogen peroxide of 0.2-0.3%, at 50-60 DEG C of decolouring 1-2h, be then warmed up to 80-90 DEG C and keep 10-20min, filter with 280-350 object tulle;
(7) CaCl
2solution-treated: filtrate slowly adds the CaCl of volume ratio 2-3% concentration 10%
2solution, leaves standstill 1-2h, then filters, with CaCl residual in fresh tap water cleaning calcium alginate fiber
2solution and other impurity;
(8) ion-exchange: calcium alginate adds 12-15 purified water doubly, then by 1-2 doubly 10% NaCl solution, carries out ion-exchange, makes calcium alginate fiber be converted into sodium alginate solution completely in 50 DEG C of water-baths;
(9) sodium alginate processed: then use the alcohol precipitation of 95%, obtains sodium alginate, and sodium alginate obtains finished product through dehydration, oven dry, pulverizing;
(10) ethanol processed: the centrifugal filtrate autoclaving in step (3), after cooling, adds activated yeast, and inoculative proportion is 15-20%, 27-35 DEG C and seals and continue to cultivate fermentation in 4-8 days, and ethanol is produced in fermented liquid distillation;
(11) seaweed organic fertilizer processed: contain a large amount of compositions such as protein, nitrogen, phosphorus, potassium, the liquid after ethanol evaporation in remaining liquid after distillation ethanol, after being concentrated to 45-60% concentration, spray is dry, granulation, prepares seaweed organic fertilizer.
2. the method for Sargassum fusiforme Middle nutrition material is extracted in a kind of dearsenification according to claim 1, it is characterized in that: fermentative production of ethanol in described step (10), after enzymolysis solution sterilizing, access activated industrial yeast bacterial classification CICC31447, carry out fermentation culture.
3. the method for Sargassum fusiforme Middle nutrition material is extracted in a kind of dearsenification according to claim 1, it is characterized in that: described step (10) fermentative production of ethanol, enzymolysis solution is through the yeast of overactivation at 30 DEG C, and fermentation culture 7 days, the bio-ethanol amount obtained is maximum.
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Cited By (5)
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| KR101900366B1 (en) * | 2017-12-26 | 2018-09-20 | 한국오오타식품주식회사 | Arsenic removal method of Hizikia fusiforme using organic acids |
| CN109566807A (en) * | 2018-11-30 | 2019-04-05 | 龚士华 | Selenium-enriched vine tea and its processing method |
| CN109566806A (en) * | 2018-11-30 | 2019-04-05 | 龚士华 | It is a kind of for promoting the sargassum fusifome extracting solution of selenium-enriched vine tea health-care effect |
| CN114634583A (en) * | 2022-03-02 | 2022-06-17 | 华南理工大学 | Alginic acid with remarkable anti-photoaging activity and preparation method and application thereof |
| CN115153021A (en) * | 2022-08-12 | 2022-10-11 | 大闽食品（漳州）有限公司 | Sargassum fusiforme extract and application thereof in lipid-lowering and sugar-lowering products |
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| CN115153021A (en) * | 2022-08-12 | 2022-10-11 | 大闽食品（漳州）有限公司 | Sargassum fusiforme extract and application thereof in lipid-lowering and sugar-lowering products |
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Application publication date: 20150211 |