Background technology
Marine alga is the low plant such as phototrophy such as grade that is grown in the ocean, is the organic original producer in ocean.Because marine alga is to be grown in this special surrounding medium of seawater, so it also contains trace elements such as the incomparable iodine of many land plants, potassium, magnesium, manganese, titanium and Sargassum polysaccharides, N.F,USP MANNITOL etc. except the nutrition that contains land plant and have.Special composition in the marine alga---Sargassum polysaccharides can not only the chelating heavy metal ion, and can increase the soil venting capability, and the effect of this soil air-conditioning is difficult for by erodsion losses such as wind, water soil.In addition, marine alga also contains miscellaneous VITAMIN, nitrogenous compound etc., is ideal organic fertilizer raw material.With marine alga or its extract is that the fertilizer of raw material is called as seaweed fertilizer, and market is called as algae essence, seaweed powder, varec abroad, has been widely used in aspects such as agricultural and gardening abroad, and domestic and abroad market prospect is very good.
At present, the marine alga fragmentation all is Mechanical Crushing or enzymatic shell-broken, extract temperature at 80-100 ℃, extraction time is generally at 4-6 hour, extraction time adopts alkalescence, neutrality or acidic solution to soak or the stirring extraction more than twice, extracts yield at 1%-3%, but impurity such as protein is more in the vat liquor, and high temperature may cause that also polysaccharide decomposes.Though can adopt sodium hydroxide and formaldehyde method etc. that frond or vat liquor are carried out pre-treatment minimizing foreign matter content, pre-treatment tends to cause polysaccharide loss to reach more than 10%.
The separation and Extraction Sargassum polysaccharides generally adopts the ethanol step-by-step precipitation method at present from algae leaching liquor.Though ethanol precipitation is easy to advantages such as scale operation, but because thereby its cardinal principle is to make the polysaccharide dehydration produce precipitation by the specific inductivity that reduces the aqueous solution to come separating polyose, almost be applicable to all water-soluble polysaccharides, though homopolysaccharide can fractional precipitation under the condition of different concentration ethanol, but specificity is not high, cause the separation selectivity of required polysaccharide relatively poor, the purity that improves polysaccharide needs to repeat precipitation through repeated multiple times, thereby cause polysaccharide loss big, reduced the rate of recovery of polysaccharide.
In addition, the extracting method of Sargassum polysaccharides flocculate in addition extraction method, the ultrasonication lixiviate of circulation gas lift-type and solvent extraction extraction method, these methods mainly are the extracting method of pharmaceutical grade Sargassum polysaccharides, the cost height, and do not consider the comprehensive utilization of marine alga, be not suitable for agriculture production.
Though increasing result of study has demonstrated Sargassum polysaccharides and had the wide development application prospect, existing Sargassum polysaccharides lixiviate and isolation technique cost height have restricted the scale operation and the widespread use of Sargassum polysaccharides.In addition, in the existing marine alga leaching process, ignored the separation and Extraction of fucoidin.
At the deficiencies in the prior art, the present inventor concentrates on studies, and found that, adopts to comprise that the method for freezing and pulverizing technology, ultrasonic wave water liquid and alkali lye lixiviate step extracts marine alga, can shorten extraction time, saves alkali lye 40-60% simultaneously.Reduced production cost, marine alga actives extraction yield has also been improved several times.In addition, take this method also can extract active ingredient substance such as phytokinin, growth hormone, Plant hormones regulators,gibberellins class material and polyphenols etc. in the marine alga comprehensively, and guarantee its biological activity.
Summary of the invention
One of purpose provided by the invention provides a kind of extracting method of fucoidin.
It is method of comprehensive utilization with marine alga that another object of the present invention provides a kind of, and it is main raw material with the marine alga, adopts the extracting method that comprises steps such as freezing and pulverizing technology, ultrasonic wave water liquid, alkali lye lixiviate.This method can be extracted institute's inherent endogenous plant-growth regulator in the marine alga to greatest extent, and keep its biological activity, isolate fucoidin simultaneously, and a last left residue is produced agricultural-food comprise all feeds and composite fertilizer, thus full use.
A further object of the present invention provides the seaweed product for agriculture that adopts method for preparing.
The invention provides a kind of method that fully utilizes marine alga, it may further comprise the steps:
1). marine alga is ground into ultramicro powder through freezing crusher.Taking liquid nitrogen is the low-temperature receiver media, carries out freezing micronizing, utilizes material under ultralow temperature conditions, and the material physico-chemical property changes, and fragility increases severely, and pulverizes, and can protect smashing fineness.
2). with marine algae powder hot water lixiviate under ultrasonic vibration, ultrasonic frequency 20-100KHz, time 20-50min filters.
3). step 2) gained filtrate, add AlCl
3Solution adds KOH solution again and generates precipitation, centrifugation, and obtaining throw out is the mixture that contains the fucoidin crude product, the treated again fucoidin that gets, the gained supernatant liquor is standby.This mixture can be with methyl alcohol or ethanol, Trisodium Citrate, CaCl
2Repeatedly handle, this method is an ordinary method, can get medicinal raw material fucoidin crude product.
4). step 2) gained filter residue KOH solution, under ultrasonic vibration, lixiviate 20-50min uses an amount of acid such as H again
2SO
4, H
3PO
4Or neutralization such as amino acid, transfer between the pH to 6-10, to the medicinal extract sample.
5). the supernatant liquor of step 3) and 4) medicinal extract sample material mixes in the lump, the metal-salt such as the CuSO of amount or trace element in adding
4, FeSO
4, ZnSO
4Deng complexing, after the complexing, add sepiolite powder, filter.Under oligomeric Sargassum polysaccharides existence condition, extracting solution of marine alga and divalent-metal ion complexing, and do not form precipitation.
The filtrate of step 5) can be prepared different products as required with filter residue.
I) the filtered liquid thin liquid adds an amount of trimethyl-glycine and fertilizer component such as potassium primary phosphate, urea etc., is mixed with the marine alga active liquid fertilizer.
Ii) liquid seaweed manure adds an amount of solubility N, P, K fertilizer component, is spray dried to solubility algae essence pulvis.
Iii) insoluble marine alga ground-slag can be re-dubbed compound fertilizer with other fertilizer components, as marine alga organic-inorganic compound mixed fertilizer, seaweed organism fertilizer etc., also can be used as fodder additives.
The present invention also provides the method for preparing product for agriculture, and it may further comprise the steps:
1). marine alga is ground into ultramicro powder through freezing crusher.Taking liquid nitrogen is the low-temperature receiver media, carries out freezing micronizing, utilizes material under ultralow temperature conditions, and the material physico-chemical property changes, and fragility increases severely, and pulverizes, and can protect smashing fineness.
2). with marine algae powder hot water lixiviate under ultrasonic vibration, ultrasonic frequency 20-100KHz, time 20-50min filters.
3). step 2) gained filtrate, add AlCl
3Solution adds KOH solution again and generates precipitation, centrifugation, and obtaining throw out is the mixture that contains the fucoidin crude product, the treated again fucoidin elaboration that gets, the gained supernatant liquor is filtrate A.
4). step 2) gained filter residue KOH solution, under ultrasonic vibration, lixiviate 20-50min gets the brown alga extracting solution.
5). the brown alga extracting solution of step 4) gained is put into reactor, the metal-salt such as the CuSO of amount or trace element in adding
4, FeSO
4, ZnSO
4Deng complexing, after the complexing, add sepiolite powder, filter, add N, P, K fertilizer again.
6). said mixture is added an amount of acid, neutralize as sulfuric acid, phosphoric acid, amino acid, transferring to solution is that 8-10 filters to PH, gets liquor B and filter residue C.
7a). get above-mentioned gained liquor B and step 3) gained filtrate A hybrid modulation, make the marine alga composite liquid fertilizer that contains endogenous seaweed plants growth regulator.This composite liquid fertilizer is doubly converted the water dilution at 400-800 and is made the crop foliage fertilizer.
The marine alga composite liquid fertilizer adds white carbon black (add-on is 10%), the drying of dusting, and sieve (80 order) is solubility algae essence pulvis.
7b). get step 6) gained filter residue C drying, cross 40 mesh sieves, can make the fertile part material of compound or, also can be used as soil conditioner as feedstuff raw material.
In specific embodiments, the method that the present invention prepares seaweed product for agriculture comprises the steps:
1). with marine alga, for example clean fresh marine alga or dry marine alga, preferred brown alga is cut into 20-40cm
2About piece, pulverize with the liquid nitrogen freezing supper micron mill.
2). above-mentioned marine algae powder is put in the immersion ultrasonic extraction device, add 60-80 ℃ of hot water, the hot water amount of adding is 4-10 a times of marine alga weight, is 10kg as marine algae powder, then hot water is the 40-100 kilogram, stir with agitator, and be the ultrasonic vibration of 20-100KHz frequency, the swing crushing alginic cell with frequency, time is 20-50 minute, filter, obtain filtrate, filter residue is standby.
3). get above-mentioned filtrate 100kg, add for example 10%AlCl of 20-50kg
3Solution mixes, and slowly adds for example 10%KOH solution of 10-40kg again, generates precipitation, filters, and gets filtrate and throw out.The gained throw out is for containing fucoidin and other sedimentary mixtures, and this mixture can be with methyl alcohol or ethanol, Trisodium Citrate, CaCl
2Repeatedly handle, this method is an ordinary method, can get medicinal raw material fucoidin crude product, can get the fucoidin 0.2-0.5kg of content at 30-60%.It is A liquid that gained filtrate is contained part marine alga actives.
4). with step 2) gained filter residue 60kg, the 10%KOH solution that adds 40-100kg, put into the ultrasonic wave extraction unit, the heated solution temperature is 60-80 ℃, heat while stirring, with the ultrasonic vibration fragmentation of 20-100KHz frequency, digestion time is 20-50 minute, and making the brown alga extracting solution is 140-200kg.
5). the brown alga extracting solution of step 4) gained is put into reactor, and every 300kg extracting solution adds 8kgFeSO
4, 5kgCuSO
4, 5kgZnSO
4, 2kgMnSO
4, the 1kg ammonium molybdate is heated to 70-120 ℃, adds the sepiolite powder of 30-50kg again, adds 10kg urea again, and the 10kg potassium primary phosphate stirs, and is incubated 1-3 hour.
6). said mixture is added an amount of acid, neutralize as sulfuric acid, phosphoric acid, amino acid, transferring to solution is that 8-10 filters to PH, gets liquor B and filter residue C.
7a). get above-mentioned gained liquor B 100kg and step 3) gained filtrate A 100-400kg hybrid modulation, make the marine alga composite liquid fertilizer that contains endogenous seaweed plants growth regulator.This composite liquid fertilizer is doubly converted the water dilution at 400-800, and farm crop are directly sprayed or irritate root.
Get gained marine alga composite liquid fertilizer and add white carbon black (add-on is 10%), the drying of dusting, sieve (80 order) is solubility algae essence pulvis.
7b). get step 6) gained filter residue C drying, cross 40 mesh sieves, can make the fertile part material of compound or make feedstuff raw material, also can be used as soil conditioner.
Marine alga of the present invention is meant that phaeophyta (as sea-tangle, mouse tail algae etc.), red algae (as the husky dish of deer horn, freeze husky dish, Mi Maosha dish etc.) or other are used for producing the algae of Sargassum polysaccharides, preferred brown alga, particularly sea-tangle.
The low-temperature receiver media that the inventive method is utilized liquid nitrogen carries out freezing micronizing, and its smashing fineness is the 1/100-1/2000 of traditional breaking method fineness.Simultaneously, adopt ultrasonic wave alkali lye microwave leaching technology, lixiviate speed shortened to 20-50 minute by 3-10 hour of traditional alkali lye lixiviate, had improved production rate greatly.Save alkali lye 40-60% simultaneously.Reduced production cost, marine alga actives extraction yield has also been improved several times.
Take the inventive method can extract active ingredient substance such as phytokinin, growth hormone, Plant hormones regulators,gibberellins class material and polyphenols etc. in the marine alga comprehensively.And guarantee its biological activity.
The seaweed fertilizer that adopts the inventive method to produce is rich in the nutritive element that is easily absorbed by crop that exists with organic and active substance that in a large number can coordinate plant growth, is a kind of environmental friend fertilizer; Has special advantages at volume increase, degeneration-resistant, natural sex with aspect having no side effect; It improves light and effect promoting crop root to grow, and aspects such as strong strain body have significant effect.The peculiar inorganic salt of seaweed fertilizer, VITAMIN, plant hormone, polyphenol, polysaccharide isoreactivity material can improve crop quality greatly, strengthen that it is disease-resistant, drought resisting, cold tolerance, and can significantly improve output.Its reasonable use will bring considerable economic for you.It can be used as the nutrition source use of soilless culture in addition, can also the powerful root nematode that suppresses in the soil.Mosaic virus restraining effect to the banded sclerotial blight of the red spider worm of warmhouse booth, paddy rice, tobacco is especially remarkable.The seaweed fertilizer that the inventive method is produced is applicable to crops such as vegetables, melon and fruit, flowers, tealeaves, tobacco, grain, cotton, oil, lawn.As a kind of new green environment protection fertilizer, it more is applicable to the use of green non-pollution vegetables base.Seaweed fertilizer is mixed use with natural humic acid salt, can play the effect of the fertile economic benefits and social benefits of medicine. and it can be re-dubbed organic-inorganic composite fertilizer with chemical fertilizer, can obviously increase fertilizer efficiency.It is improving Soil structure, increases the ventilative water retention capacity of soil, prevents that aspect effect such as soil property deterioration is remarkable.It is a kind of good agricultural chemicals dilution synergistic agent by physics effect and special agricultural chemicals formation complex body.The existence of polysaccharide in the seaweed fertilizer has stronger sticking power during with most of combined use of pesticides, can significantly improve drug effect, prolong the drug effect phase.
Embodiment
Hereinafter the mode with indefiniteness embodiment provides optimal way of the invention process.
Embodiment 1
Product for agriculture of the present invention adopts the following steps preparation:
1). clean fresh brown alga is cut into 20-40cm
2About piece, with liquid nitrogen freezing supper micron mill (size reduction machinery company limited of DFZ-2 type Jiangyin City gold section)-120--140 ℃ pulverize at low temperature.
2). above-mentioned marine algae powder 10kg is put into immersion ultrasonic extraction device (ultrasonic equipment company is given birth to by TY type KS and sea, KS-C type Ningbo daybreak section) lining, add 40 kilograms of 60 ℃ of hot water, stir with agitator, and be the ultrasonic vibration of 100KHz frequency with frequency, the swing crushing alginic cell, the time is 30 minutes, filters, obtain filtrate, filter residue is standby.
3). get above-mentioned filtrate 100kg, add 10% the AlCl of 20kg
3Solution mixes, and slowly adds the KOH solution of 20kg 10% again, generates precipitation, filters, and gets filtrate and throw out, and the gained throw out is for containing fucoidin and other sedimentary mixtures.This mixture can be with methyl alcohol or ethanol, Trisodium Citrate, CaCl
2Repeatedly handle, this method is an ordinary method, can get medicinal raw material fucoidin crude product, can get content at 50% fucoidin 0.25kg, and it is A liquid that gained filtrate is contained part marine alga actives.
4). with step 2) gained filter residue 60kg, the 10%KOH solution of adding 40kg is put into the ultrasonic wave extraction unit, the heated solution temperature is 60 ℃, heats while stirring, with the ultrasonic vibration fragmentation of 100KHz frequency, digestion time is 30 minutes, and making the brown alga extracting solution is 150k9.
5). the brown alga extracting solution of step 4) gained is put into reactor, and every 300kg extracting solution adds 8kg FeSO
4, 5kg CuSO
4, 5kg ZnSO
4, 2kg MnSO
4, the 1kg ammonium molybdate is heated to 80 ℃, adds the sepiolite powder of 30kg again, adds 10kg urea again, and the 10kg potassium primary phosphate stirs, and is incubated 3 hours.
6). said mixture is added an amount of amino acid neutralize, transferring to solution is that 8-10 filters to pH, gets liquor B and filter residue C.
7a). get above-mentioned gained liquor B 100kg and step 3) gained filtrate A 200kg hybrid modulation, make the marine alga composite liquid fertilizer that contains endogenous seaweed plants growth regulator, this composite liquid fertilizer is doubly converted the water dilution at 400-800 and is made the crop foliage fertilizer.
Gained marine alga composite liquid fertilizer adds white carbon black (add-on is 10%), the drying of dusting, and sieve (80 order) is solubility algae essence pulvis.
7b). get step 6) gained filter residue C drying, cross 40 mesh sieves, can make the fertile part material of compound or make feedstuff raw material, also can be used as soil conditioner.
Embodiment 2
Product for agriculture of the present invention adopts following method preparation:
1). clean dry brown alga is cut into 20-40cm
2About piece, with-120~-140 ℃ of pulverize at low temperature of liquid nitrogen freezing supper micron mill (size reduction machinery company limited of DFZ-2 type Jiangyin City gold section).
2). above-mentioned marine algae powder 10kg is put into immersion ultrasonic extraction device (ultrasonic equipment company is given birth to by TY type KS and sea, KS-C type Ningbo daybreak section) lining, add 100 kilograms of 80 ℃ of hot water, stir with agitator, and be the ultrasonic vibration of 50KHz frequency with frequency, the swing crushing alginic cell, the time is 50 minutes, filters, obtain filtrate, filter residue is standby.
3). get above-mentioned filtrate 100kg, add 10% the AlCl of 50kg
3Solution mixes, and slowly adds the KOH solution of 30kg 10% again, generates precipitation, filter, filtrate and throw out, the gained throw out is for containing fucoidin and other sedimentary mixtures, this mixture can be with methyl alcohol or ethanol, Trisodium Citrate, CaCl
2Repeatedly handle, this method is an ordinary method, can get medicinal raw material fucoidin crude product, can get content at 30% fucoidin 0.5kg, and it is A liquid that gained filtrate is contained part marine alga actives.
4). with step 2) gained filter residue 60kg, the 10%KOH solution of adding 80kg is put into the ultrasonic wave extraction unit, the heated solution temperature is 80 ℃, heats while stirring, with the ultrasonic vibration fragmentation of 50KHz frequency, digestion time is 30 minutes, and making the brown alga extracting solution is 200kg.
5). the brown alga extracting solution of step 4) gained is put into reactor, and every 300kg extracting solution adds 8kg FeSO
4, 5kg CuSO
4, 5kg ZnSO
4, 2kg MnSO
4, the 1kg ammonium molybdate is heated to 70-100 ℃, adds the sepiolite powder of 50kg again, adds 10kg urea again, and the 10kg potassium primary phosphate stirs, and is incubated 2 hours.
6). said mixture is added an amount of phosphoric acid neutralize, transferring to solution is that 8-10 filters to pH, gets liquor B and filter residue C.
7a). get above-mentioned gained liquor B 100kg and step 3) gained filtrate A 400kg hybrid modulation, make the marine alga composite liquid fertilizer that contains endogenous seaweed plants growth regulator, this composite liquid fertilizer is doubly converted the water dilution at 400-800 and is made the crop foliage fertilizer.
Get the marine alga composite liquid fertilizer and add white carbon black (add-on is 10%), the drying of dusting, sieve (80 order) is solubility algae essence pulvis.
7b). get step 6) gained filter residue C drying, cross 40 mesh sieves, can make the fertile part material of compound or make feedstuff raw material, also can be used as soil conditioner.