A kind of two marine alga fertilizers and preparation method thereof
Technical field
The present invention relates to seaweed fertilizer field, be specifically related to a kind of two marine alga fertilizers and preparation method thereof.
Background technology
Since the eighties in 20th century, efficient marine alga fertilizer suitability for industrialized production was come out, seaweed fertilizer is fast-developing in the world with the characteristic of its comprehensive nutrition, unique effect, natural nuisance-free and very high cost performance, and is given priority to and promote in a lot of countries.
Mostly current seaweed fertilizer is on the market to produce take brown alga as single starting material.Lalgine composition in brown alga is proved to be a kind of natural soil conditioning material in recent years, can promote the formation of soil aggregate, improve soil internal void space, increase the ability of soil fertilizer water conservation guarantor gas, the colloid balance of recovering rapidly soil, increases soil organisms vigor.Lalgine foliage-spray in seaweed fertilizer can also reduce the surface tension of water, forms thin film at plant surface, and enlarge active surface promotes the absorption of various nutritive substances in seaweed fertilizer.
Enteromorpha is a kind of large-scale economic green alga, is commonly called as tongue bar, sea sedge, is Chlorophyta Ulvales Ulvaceae plant.Since 2008, the enrichment of Deposits in Eastern Coastal China large-scale outbreak Enteromorpha green alga resource, a large amount of Enteromorpha resources of assembling, have had a strong impact on coastal resident's life and city management.In this case; sea, Qingdao mcroorganism Group Co.,Ltd is according to the Biological characteristics of Enteromorpha; research and develop the method for a whole set of Enteromorpha resource extent processing, successfully carried out the collection (granted patent: ZL200910313001.0 Enteromorpha method for innocent treatment and equipment thereof) of Enteromorpha resource.2008 so far, and our company is devoted to the comprehensive utilization of Enteromorpha resource always.Wherein, the Enteromorpha marine alga fertilizer take Enteromorpha as development of raw materials, has obtained national inventing patent mandate, patent name: the preparation method of the extractive technique of Enteromorpha activeconstituents and Enteromorpha seaweed fertilizer, the patent No.: ZL200910014719.X.This patent of invention provides technical support for the application of green alga in seaweed fertilizer, and Enteromorpha seaweed fertilizer is sold on market at present.
Experiment shows, the brown alga take sea-tangle and Enteromorpha as representative and green alga are applied in seaweed fertilizer and respectively have superiority.It is not yet seen that two kinds of marine algas are used simultaneously produces the seaweed fertilizer with two algae synergies and asks city.Therefore how by reasonably combined the degraded of these two kinds of marine algas, producing two algae extracts with synergy, is the problem that the present invention will face for the production of seaweed fertilizer.
Summary of the invention
The object of the present invention is to provide a kind of two marine alga fertilizers and preparation method thereof, the described pair of seaweed fertilizer is take brown alga and green alga as raw material, and described pair of marine alga fertilizer specifically comprises the two algae complex polysaccharide fertilizer additives that utilize two marine alga coordinated enzymatic hydrolysis technology to prepare; The two marine alga organic granular fertilizers that utilize two marine alga slags to prepare; Utilize two marine alga complex polysaccharides to extract two Trace Elements In Seaweeds fertilizer prepared by waste liquid.
For achieving the above object, the present invention is achieved by the following technical solutions:
A preparation method for pair marine alga fertilizer, it comprises the following steps:
1) pre-treatment of two marine algas: described pair of marine alga is green alga and brown alga,
Fresh green alga is through pre-treatment, and extrusion dehydration to water content is 50-60%, freeze thawing 2-3 time; Fresh brown alga drains after surface-moisture, is cut into 2-3cm fritter, freeze thawing 2-3 time;
Or, after dry green alga and dry brown alga pulverize and sieve, add 5-8 times of water, after thoroughly infiltrating, freeze thawing 2-3 time, makes green alga paste and brown alga and sticks with paste;
2) extraction of two Sargassum polysaccharides:
Two marine alga coordinated enzymatic hydrolysis: getting described fresh green alga and brown alga after freeze thawing, or get described green alga paste and brown alga paste after freeze thawing, is that 1:2-2:1 is dropped into reactor according to the mass ratio of green alga and brown alga, adds and accounts for marine alga quality 10-15 water doubly;
Add again the prozyme that accounts for marine alga total mass 2%-3%, regulatory enzyme enzymatic hydrolysis system PH is 3.5-4.5, keeping enzymatic hydrolysis system temperature is 40-55 ℃, enzymolysis 1.5-2 hour, after add the polysaccharide degrading enzyme that accounts for marine alga total mass 1-2%, adjustment system PH is 5.5-6.5, and two Sargassum polysaccharides are carried out to specificity degraded, makes its molecular weight by 50 × 10
4-60 × 10
4d is degraded to 10 × 10
4-20 × 10
4the active polysaccharide fragment of D, obtains two marine alga enzymolysis solutions and two marine alga slag through centrifugation while hot;
3) preparation of marine alga fertilizer
Two marine alga slags after enzymolysis, through drying after granulation, prepare two marine alga organic granular fertilizers; Two marine alga enzymolysis solutions after centrifugal, getting molecular weight is 10,000-100,000 daltonian pairs Sargassum polysaccharides, carries out ultrafiltration, prepares two Sargassum polysaccharides concentrated solutions, makes two Sargassum polysaccharides fertilizer additives after lyophilize.
Further improvement to technique scheme: the green alga described in described step 1) is Enteromorpha and/or sea lettuce; Described brown alga is at least one in sea-tangle, sargassun, bladder wrack.
Further improvement to technique scheme: in described step 1), freeze thawing all adopts after-4 ℃ of cold house's precoolings ,-30 ℃ after the quick freezing 5-6 of cold house hour, freezing after, use steam thawing.
Further improvement to technique scheme: described step 2) described in prozyme be selected from one or more in cellulase, proteolytic enzyme, polygalacturonase, total enzyme work of prozyme is 3 × 10
4-8 × 10
4iU.
Further improvement to technique scheme: in described step 3), bake out temperature remains on 80-95 ℃, through shear granulation, control particle diameter is 2-3mm.
Further improvement to technique scheme: the waste liquid in described step 3) after ultrafiltration prepares two complete micro-foliage fertilizers of marine alga after reverse osmosis membrane is concentrated.
Further improvement to technique scheme: the pretreated method of fresh green alga described in described step 1) is: the fresh green alga extrusion dehydration baling equipment of just salvaging disembarkation is carried out to extrusion dehydration, first slough the free-water of 20-30% left and right, water content is down to 60-70%, and volume-diminished is original 1/4 ~ 1/5; With shears, by green alga fragmentation, the free-water in releasing structure, then carries out secondary extrusion dehydration, makes water content be down to 50%-60%.
Further improvement to technique scheme: the dry green alga in described step 1) and the water content of dry brown alga are below 10%, pulverizes, and crosses 60 order-100 mesh sieves and obtains chlorella powder and brown alga powder.
The present invention also provides the two marine alga fertilizers that utilize described preparation method to make.
Described pair of marine alga fertilizer specifically comprises the two algae complex polysaccharide fertilizer additives that utilize two marine alga coordinated enzymatic hydrolysis to prepare; The two marine alga organic granular fertilizers that utilize two marine alga slags to prepare; Utilize two marine alga complex polysaccharides to extract two Trace Elements In Seaweeds foliage fertilizers prepared by waste liquid.
Compared with prior art, advantage of the present invention and positively effect are:
1, the present invention utilizes modern biotechnology to extract in brown alga and green alga activeconstituents for the preparation of novel alga fertilizer.Adopt multigelation method to carry out pre-treatment to marine alga.Through multigelation, the ice crystal that alginic cell wall is formed in cell punctures, and makes the consumption of follow-up enzymolysis process enzyme be reduced to 2-3% by 5-8%, and enzymolysis time was reduced to 1.5-2 hour by 3-4 hour, was conducive to the raising of effective component extraction rate.
2, the present invention adopts two marine alga coordinated enzymatic hydrolysis technology, carries out the extraction of two marine alga active polysaccharides.First adopt prozyme to degrade to two marine algas, destroy two seaweed fiber Constituent cell walls, Sargassum polysaccharides is discharged, then add complex polysaccharide degrading enzyme, two Sargassum polysaccharides are degraded targetedly, making it be degraded to molecular weight is 10 × 10
4-20 × 10
4daltonian polysaccharide fragment.Thereby the active group of polysaccharide is more exposed, improve action effect.
3, the present invention adopts ultra-filtration technique to separate two marine alga enzymolysis solutions, by active polysaccharide fragment, from two marine alga enzymolysis solutions, concentrating and separating is out, from production technique angle, both realized the separation of activeconstituents, realize again the concentrated of active polysaccharide, change traditional evaporating and concentrating process, saved energy consumption and reduced again production cost.
4, the present invention has carried out appropriate processing to the two marine alga slags and the ultrafiltration waste liquid that produce in degraded leaching process.Shear by oven dry, realized the preparation of the marine alga organic granular fertilizer of high organic content; By the reverse osmosis concentration to ultrafiltration waste liquid, produce the complete micro-foliage fertilizer of two marine algas of small-molecule active substances such as being rich in various trace elements in two marine algas and amino acid, N.F,USP MANNITOL.Realize the full use of various nutritive ingredients in two marine algas.
In conjunction with reading after the specific embodiment of the present invention, it is clearer that the other features and advantages of the invention will become.
embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
The preparation method of of the present invention pair of marine alga fertilizer comprises the following steps:
1, marine alga pre-treatment
Adopt the method described in patent " ZL200910313001.0 Enteromorpha method for innocent treatment and equipment thereof " to process fresh Enteromorpha: the fresh Enteromorpha extrusion dehydration baling equipment of just salvaging disembarkation is carried out to extrusion dehydration, slough the free-water of 20-30%, be down to 60-70% containing water-content, volume-diminished is original 1/4 ~ 1/5; By Enteromorpha fragmentation, discharge the free-water in Enteromorpha tubular structure with shears, then carry out secondary extrusion dehydration, make water content be down to 50%, for subsequent use.
After Fresh Laminaria Japonica drains away the water, be cut into the fritter of 2cm left and right through shears, for subsequent use.
By the Enteromorpha of above-mentioned processing and sea-tangle, be first placed in-4 ℃ of cold house's precoolings after 2-3 hour, proceed to after-30 ℃ of freezing 4-5 in quick-frozen chamber hours, take out, be placed in vaporium and thaw.Repeat after 2 times, for subsequent use.
2, the extraction of two Sargassum polysaccharides
Get above-mentioned fresh Enteromorpha and sea-tangle 200Kg after freeze thawing, drop into reactor, add 2200Kg water, (prozyme is selected from one or more in cellulase, proteolytic enzyme, polygalacturonase, and the enzyme work of prozyme is 3 × 10 to add 4Kg prozyme
4-8 × 10
4iU), regulatory enzyme enzymatic hydrolysis system PH is 4.0, is warming up to 45 ℃, stirs 1.5 hours, adds 2Kg polysaccharide degrading enzyme, and adjusting system PH is 6.0, is warming up to 50 ℃, continues to stir 1 hour, obtains two marine alga enzymolysis solutions and two marine alga slag while hot through centrifugation.
3, the preparation of two marine alga fertilizers
Two marine alga slag dryings are during to moisture content 60% left and right, by shearing, after granulation, prepare two seaweed organic fertilizer particles, continue to dry to moisture be 22%, pack out finished product.After testing, record the index content of this pair of marine alga organic granular fertilizer as follows:
Project | Nitrogen | Phosphorus | Potassium | Organic | Sargassum polysaccharides |
Content % | 2% | 0.06% | 3.1% | 75% | 3.0% |
Two marine alga enzymolysis solutions are through high-performance liquid chromatogram determination, and 7 fragments appear altogether in two Sargassum polysaccharides between molecular weight 100,000-300,000, and therefore selecting molecular weight is that 100,000 ultra-filtration membrane carries out ultrafiltration and concentration, finally obtains two Sargassum polysaccharides extracting solutions.Detect through phenol sulfuric acid process, the two polysaccharides content in two Sargassum polysaccharides extracting solutions are 22.31%.This extracting solution, through lyophilize, prepares two Sargassum polysaccharides powdered fertilizer additives, can be used for the interpolation of various marine alga fertilizers.Result is as follows after testing for two Sargassum polysaccharides powdered fertilizer additives:
Project | Polysaccharide | Lalgine | Sulfate radical |
Content % | 62.3% | 20.1% | 36.5% |
The interpolation of the multiple fertilizer such as the described pair of Sargassum polysaccharides fertilizer additive can be for comprising granular fertilizer, rush fertilising, foliage fertilizer, powdery fertilizer.
Ultrafiltration waste liquid makes two complete micro-foliage fertilizers of algae after reverse osmosis membrane is concentrated.Detect through atomic absorption spectrophotometer, the content that records each element is as follows:
Project | Copper | Iron | Manganese | Zinc | Boron | Molybdenum | Calcium | Magnesium | Amino acid |
Content g/L | 9.7 | 6.2 | 5.1 | 15 | 3 | 0.52 | 15 | 9.3 | 36.8 |
Embodiment 2
Of the present invention pair of marine alga fertilizer specifically can also make by following steps:
1, marine alga pre-treatment
Adopt the method described in patent " ZL200910313001.0 Enteromorpha method for innocent treatment and equipment thereof " to process fresh Enteromorpha: the fresh Enteromorpha extrusion dehydration baling equipment of just salvaging disembarkation is carried out to extrusion dehydration, slough the free-water of 20-30% left and right, be down to 60-70% containing water-content, volume-diminished is original 1/4 ~ 1/5; By Enteromorpha fragmentation, discharge the free-water in Enteromorpha tubular structure with shears, then carry out secondary extrusion dehydration, make water content be down to 50%, now utilize hot blast to carry out air stream drying dehydration, water-content is down to below 10%, utilize the cyclonic separator impurity elimination of removing sand; Finally enter pulverizer and pulverize, so far realize the harmless treatment of Enteromorpha, obtain waterside lichenin after 60 mesh sieves.
Sargassun is dried and pulverized, cross 60 mesh sieves and obtain sargassun powder.
After waterside lichenin and sargassun powder are mixed according to 1:1 ratio.Add the water of 5 times of volumes, after fully infiltrating, freeze thawing 2-3 time, in the pasty state.
2, the extraction of two Sargassum polysaccharides
Get above-mentioned two marine algas after freeze thawing and stick with paste 1000Kg, drop into reactor, add 1200Kg water, add 2Kg prozyme, regulatory enzyme enzymatic hydrolysis system PH is between 4.0, be warming up to 45 ℃, stir 1.5 hours, add 2Kg polysaccharide degrading enzyme, adjustment system PH is 6.0, be warming up to 50 ℃, continue to stir 1 hour, separate to obtain two marine alga enzymolysis solutions and two marine alga slag through centrifugal (whizzer is butterfly centrifugal machine or horizontal spiral centrifuge) while hot;
3, the preparation of two marine alga fertilizers
Two marine alga enzymolysis solutions are through high-performance liquid chromatogram determination, and 10 fragments appear altogether in two Sargassum polysaccharides between molecular weight 80,000-300,000, and therefore selecting molecular weight is that 50,000 ultra-filtration membrane carries out ultrafiltration and concentration, finally obtains two Sargassum polysaccharides extracting solutions.Detect through phenol sulfuric acid process, the two polysaccharides content in two Sargassum polysaccharides extracting solutions are 25.01%.This extracting solution, through lyophilize, prepares two Sargassum polysaccharides powdered fertilizer additives, can be used for the interpolation of various marine alga fertilizers.Result is as follows after testing for two Sargassum polysaccharides powdered fertilizer additives:
Project | Polysaccharide | Lalgine | Sulfate radical |
Content % | 65.2% | 30.1% | 30.4% |
Ultrafiltration waste liquid makes two complete micro-foliage fertilizers of algae after reverse osmosis membrane is concentrated.Detect through atomic absorption spectrophotometer, the content that records each element is as follows:
Project | Copper | Iron | Manganese | Zinc | Boron | Molybdenum | Calcium | Magnesium | Amino acid |
Content g/L | 5.3 | 4.2 | 3.5 | 19.8 | 4.2 | 0.35 | 20.0 | 10.0 | 40.5 |
Embodiment 3
Of the present invention pair of marine alga fertilizer specifically can also make by following steps:
1, marine alga pre-treatment
Get drying bladder wrack and sea lettuce, after oven dry, pulverize, cross 60 mesh sieves, obtain bladder wrack powder and ulva lactuca powder.
After bladder wrack powder and ulva lactuca powder are mixed according to 2:1 ratio.Add the water of 3 times of volumes, after fully infiltrating, freeze thawing 2-3 time, in the pasty state.
2, the extraction of two Sargassum polysaccharides
Get above-mentioned two marine algas after freeze thawing and stick with paste 1000Kg, drop into reactor, add 1200Kg water, add 2Kg prozyme, regulatory enzyme enzymatic hydrolysis system PH is between 4.0, be warming up to 45 ℃, stir 1.5 hours, add 2Kg polysaccharide degrading enzyme, adjustment system PH is 6.0, be warming up to 50 ℃, continue to stir 1 hour, obtain two marine alga enzymolysis solutions and two marine alga slag through centrifugation while hot.
3, the preparation of two marine alga fertilizers
Two marine alga enzymolysis solutions are through high-performance liquid chromatogram determination, and 5 fragments appear altogether in two Sargassum polysaccharides between molecular weight 150,000-300,000, and therefore selecting molecular weight is that 100,000 ultra-filtration membrane carries out ultrafiltration and concentration, finally obtains two Sargassum polysaccharides extracting solutions.Detect through phenol sulfuric acid process, the two polysaccharides content in two Sargassum polysaccharides extracting solutions are 18.26%.This extracting solution, through lyophilize, prepares two Sargassum polysaccharides powdered fertilizer additives, can be used for the interpolation of various marine alga fertilizers.Result is as follows after testing for two Sargassum polysaccharides powdered fertilizer additives:
Project | Polysaccharide | Lalgine | Sulfate radical |
Content % | 45.2% | 15.6% | 28.6% |
Ultrafiltration waste liquid makes two complete micro-foliage fertilizers of algae after reverse osmosis membrane is concentrated.Detect through atomic absorption spectrophotometer, the content that records each element is as follows:
Project | Copper | Iron | Manganese | Zinc | Boron | Molybdenum | Calcium | Magnesium | Amino acid |
Content g/L | 6.9 | 5.2 | 0.6 | 11.6 | 5.2 | 0.65 | 16.2 | 11.8 | 25.5 |
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although the present invention is had been described in detail with reference to previous embodiment, for the person of ordinary skill of the art, the technical scheme that still can record previous embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of the present invention's technical scheme required for protection.