CN103771918B - A kind of two marine alga fertilizer and preparation method thereof - Google Patents

A kind of two marine alga fertilizer and preparation method thereof Download PDF

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CN103771918B
CN103771918B CN201410021767.2A CN201410021767A CN103771918B CN 103771918 B CN103771918 B CN 103771918B CN 201410021767 A CN201410021767 A CN 201410021767A CN 103771918 B CN103771918 B CN 103771918B
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alga
marine alga
fertilizer
marine
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CN103771918A (en
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单俊伟
刁红霞
王海华
李海生
宋海妹
李秀珍
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Qingdao Haida biological Group Co.,Ltd.
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QINGDAO SEAWIN BIOTECH GROUP Co Ltd
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Abstract

The invention provides a kind of two marine alga fertilizer and preparation method thereof, described preparation method comprises the pre-treatment of green alga and brown alga; The extraction of two Sargassum polysaccharides: add polysaccharide degrading enzyme after complex enzyme hydrolysis, carries out selective degradation to two Sargassum polysaccharides, makes its degrading activity polysaccharide fragment, obtains two marine alga enzymolysis solutions and two marine alga slag while hot through centrifugation; Enzymolysis solution prepares two Sargassum polysaccharides fertilizer additive after ultrafiltration, and ultrafiltration waste liquid prepares two complete micro-foliage fertilizer of marine alga after reverse osmosis concentration, and the two marine alga slags after enzymolysis, after drying granulation, prepare two marine alga organic granular fertilizer.The present invention utilizes modern biotechnology to extract activeconstituents in brown alga and green alga and, for the preparation of novel alga fertilizer, improves the extraction yield of effective constituent in two marine alga, degrade targetedly to two Sargassum polysaccharides, improve action effect; And the two algae resource of full use, prepare two polysaccharides fertilizer additive, two marine alga organic granular fertilizer and the complete micro-foliage fertilizer of two marine alga simultaneously.

Description

A kind of two marine alga fertilizer and preparation method thereof
Technical field
The present invention relates to seaweed fertilizer field, be specifically related to a kind of two marine alga fertilizer 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 its comprehensive nutrition, effect of uniqueness, the characteristic of natural nuisance-free and very high cost performance, and is given priority in a lot of country and promote.
Mostly current seaweed fertilizer is on the market with brown alga to be that single starting material are produced.Lalgine composition in brown alga is proved to be a kind of natural soil conditioning material in recent years, the formation of soil aggregate can be promoted, improve soil internal void space, increase the ability that soil fertilizer water conservation protects gas, the colloid balance of rapid recovery soil, increases soil organisms vigor.Lalgine foliage-spray in seaweed fertilizer can also reduce the surface tension of water, forms thin film, enlarge active surface at plant surface, promotes the absorption of various nutritive substance in seaweed fertilizer.
Enteromorpha is a kind of large-scale economic green alga, and being commonly called as tongue bar, sea sedge, is Chlorophyta Ulvales Ulvaceae plant.Since 2008, Deposits in Eastern Coastal China large-scale outbreak Enteromorpha green alga resource concentration, a large amount of Enteromorpha resource of assembling, has had a strong impact on life and the city management of coastal resident.In this case; Qingdao Seawin Biotech Group Co., Ltd. is according to the Biological characteristics of Enteromorpha; research and develop the method for a whole set of Enteromorpha resource extent process, be successfully made 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, take Enteromorpha as the Enteromorpha marine alga fertilizer of development of raw materials, obtained national inventing patent mandate, patent name: the extractive technique of Enteromorpha activeconstituents and the preparation method of Enteromorpha seaweed fertilizer, the patent No.: ZL200910014719.X.This patent of invention is that the application of green alga in seaweed fertilizer provides technical support, and current Enteromorpha seaweed fertilizer is commercially sold.
Experiment shows, the brown alga being representative with sea-tangle and Enteromorpha and green alga are applied in seaweed fertilizer and respectively have superiority.It is not yet seen that the seaweed fertilizer that two kinds of marine algas use production to have two algae synergy simultaneously asks city.Therefore how by reasonably combined for the degraded of these two kinds of marine algas, produce two algae extracts with synergy, for the production of seaweed fertilizer be the present invention will faced by problem.
Summary of the invention
The object of the present invention is to provide a kind of two marine alga fertilizer and preparation method thereof, the described pair of seaweed fertilizer is with brown alga and green alga for raw material, and described pair of marine alga fertilizer specifically comprises the two algae complex polysaccharide fertilizer additives utilizing two marine alga coordinated enzymatic hydrolysis technology to prepare; Utilize two marine alga organic granular fertilizers prepared by two marine alga slag; The two Trace Elements In Seaweeds utilizing two marine alga complex polysaccharide extraction waste liquid to prepare are fertile.
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 alga: 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; After fresh brown alga drains surface-moisture, be 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, obtained green alga is stuck with paste and brown alga is stuck with paste;
2) extraction of two Sargassum polysaccharides:
Two marine alga coordinated enzymatic hydrolysis: get described fresh green alga after freeze thawing and brown alga, or get the described green alga after freeze thawing and to stick with paste and brown alga is stuck with paste, be that 1:2-2:1 is dropped into reactor according to the mass ratio of green alga and brown alga, add the water accounting for marine alga quality 10-15 times;
Add the prozyme accounting for marine alga total mass 2%-3% again, regulatory enzyme enzymatic hydrolysis system PH is 3.5-4.5, enzymatic hydrolysis system temperature is kept to be 40-55 DEG C, enzymolysis 1.5-2 hour, after add the polysaccharide degrading enzyme accounting for marine alga total mass 1-2%, adjustment system PH is 5.5-6.5, carries out selective degradation to two Sargassum polysaccharides, 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, after drying granulation, prepare two marine alga organic granular fertilizer; Two marine alga enzymolysis solutions after centrifugal, getting molecular weight is 10,000-10 ten thousand daltonian pairs of Sargassum polysaccharides, carries out ultrafiltration, prepares two Sargassum polysaccharides concentrated solution, obtained two Sargassum polysaccharides fertilizer additive 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: after freeze thawing all adopts-4 DEG C of cold house's precoolings in described step 1), after cold house quick freezing 5-6 hour, after freezing, uses steam thawing for-30 DEG C.
Further improvement to technique scheme: described step 2) described in prozyme be selected from cellulase, proteolytic enzyme, polygalacturonase one or more, 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 DEG C, 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 fertilizer 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 just salvaging disembarkation is carried out extrusion dehydration, first slough the free-water of about 20-30%, water content is down to 60-70%, and volume-diminished is original 1/4 ~ 1/5; With shears, green alga is broken, 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 less than 10%, pulverizes, and crosses 60 order-100 mesh sieves and obtains chlorella powder and brown alga powder.
Two marine alga fertilizer that the preparation method that present invention also offers described in utilization obtains.
Described pair of marine alga fertilizer specifically comprises the two algae complex polysaccharide fertilizer additives utilizing two marine alga coordinated enzymatic hydrolysis to prepare; Utilize two marine alga organic granular fertilizers prepared by two marine alga slag; Utilize two Trace Elements In Seaweeds foliage fertilizers prepared by two marine alga complex polysaccharide extraction 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.Multigelation method is adopted to carry out pre-treatment to marine alga.Through multigelation, alginic cell wall is punctured by the ice crystal formed in cell, and make the consumption of follow-up enzymolysis process enzyme be reduced to 2-3% by 5-8%, 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 polysaccharide.Namely first adopt prozyme to degrade to two marine alga, destroy two seaweed fiber Constituent cell wall, Sargassum polysaccharides is discharged, then adds complex polysaccharide degrading enzyme, degrade targetedly to two Sargassum polysaccharides, making it be degraded to molecular weight is 10 × 10 4-20 × 10 4daltonian polysaccharide fragment.Thus the active group of polysaccharide is more exposed, improve action effect.
3, the present invention adopts ultra-filtration technique to be separated two marine alga enzymolysis solution, by active polysaccharide fragment, from two marine alga enzymolysis solution, concentrating and separating is out, from production technique angle, both the separation of activeconstituents had been achieved, achieve again the concentrated of active polysaccharide, change traditional evaporating and concentrating process, namely save energy consumption and again reduce production cost.
4, the present invention has carried out appropriate process to the two marine alga slag produced in degraded leaching process and ultrafiltration waste liquid.Shearing by drying, achieving 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 being rich in various trace element and the small-molecule active substance such as amino acid, N.F,USP MANNITOL in two marine alga.Achieve the full use of various nutritive ingredient in two marine alga.
After reading the specific embodiment of the present invention, the other features and advantages of the invention will become clearly.
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
The method described in patent " ZL200910313001.0 Enteromorpha method for innocent treatment and equipment thereof " is adopted to process fresh Enteromorpha: the fresh Enteromorpha extrusion dehydration baling equipment just salvaging disembarkation is carried out 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; With shears, Enteromorpha is broken, the free-water in release Enteromorpha tubular structure, then carries out secondary extrusion dehydration, makes water content be down to 50%, for subsequent use.
After Fresh Laminaria Japonica drains away the water, be cut into the fritter of about 2cm through shears, for subsequent use.
By the Enteromorpha of above-mentioned process and sea-tangle, be first placed in-4 DEG C of cold house's precoolings after 2-3 hour, after proceeding to-30 DEG C of freezing 4-5 in quick-frozen room hours, take out, be placed in vaporium and thaw.After repeating 2 times, for subsequent use.
2, the extraction of two Sargassum polysaccharides
Get above-mentioned fresh Enteromorpha after freeze thawing and sea-tangle 200Kg, 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 DEG C, stirs 1.5 hours, adds 2Kg polysaccharide degrading enzyme, and adjustment system PH is 6.0, is warming up to 50 DEG C, continues stirring 1 hour, obtains two marine alga enzymolysis solutions and two marine alga slag while hot through centrifugation.
3, the preparation of two marine alga fertilizer
Two marine alga slag drying to moisture content about 60% time, by shearing, after granulation, prepare two seaweed organic fertilizer particle, continuing to dry to moisture is 22%, packs out finished product.After testing, the index content recording this pair of marine alga organic granular fertilizer is as follows:
Project Nitrogen Phosphorus Potassium Organic Sargassum polysaccharides
Content % 2% 0.06% 3.1% 75% 3.0%
Two marine alga enzymolysis solution is through high-performance liquid chromatogram determination, and two Sargassum polysaccharides occurs 7 fragments altogether between molecular weight 100,000-30 ten thousand, therefore select molecular weight be 100,000 ultra-filtration membrane carry out ultrafiltration and concentration, finally obtain two Sargassum polysaccharides extracting solution.Detect through Phenol sulfuric acid procedure, the two polysaccharides content in two Sargassum polysaccharides extracting solution are 22.31%.This extracting solution, through lyophilize, prepares two Sargassum polysaccharides powdered fertilizer additive, can be used for the interpolation of various marine alga fertilizer.Result is as follows after testing for two Sargassum polysaccharides powdered fertilizer additive:
Project Polysaccharide Lalgine Sulfate radical
Content % 62.3% 20.1% 36.5%
Described pair of Sargassum polysaccharides fertilizer additive may be used for the interpolation comprising the multiple fertilizer such as granular fertilizer, punching fertilising, foliage fertilizer, powdery fertilizer.
Ultrafiltration waste liquid is obtained two complete micro-foliage fertilizer of algae after reverse osmosis membrane is concentrated.Detect through atomic absorption spectrophotometer, the content recording 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 be obtained by following steps:
1, marine alga pre-treatment
The method described in patent " ZL200910313001.0 Enteromorpha method for innocent treatment and equipment thereof " is adopted to process fresh Enteromorpha: the fresh Enteromorpha extrusion dehydration baling equipment just salvaging disembarkation is carried out extrusion dehydration, slough the free-water of about 20-30%, be down to 60-70% containing water-content, volume-diminished is original 1/4 ~ 1/5; With shears, Enteromorpha is broken, the free-water in release Enteromorpha tubular structure, then carries out secondary extrusion dehydration, makes water content be down to 50%, now utilize hot blast to carry out air stream drying dehydration, make water-content be down to less than 10%, utilizes cyclonic separator to remove sand impurity elimination; Finally enter pulverizer to pulverize, so far realize the harmless treatment of Enteromorpha, obtain waterside lichenin after 60 mesh sieves.
Sargassun is dried and pulverizes, 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 DEG C, stir 1.5 hours, add 2Kg polysaccharide degrading enzyme, adjustment system PH is 6.0, be warming up to 50 DEG C, continue stirring 1 hour, be separated 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 fertilizer
Two marine alga enzymolysis solution is through high-performance liquid chromatogram determination, and two Sargassum polysaccharides occurs 10 fragments altogether between molecular weight 80,000-30 ten thousand, therefore select molecular weight be 50,000 ultra-filtration membrane carry out ultrafiltration and concentration, finally obtain two Sargassum polysaccharides extracting solution.Detect through Phenol sulfuric acid procedure, the two polysaccharides content in two Sargassum polysaccharides extracting solution are 25.01%.This extracting solution, through lyophilize, prepares two Sargassum polysaccharides powdered fertilizer additive, can be used for the interpolation of various marine alga fertilizer.Result is as follows after testing for two Sargassum polysaccharides powdered fertilizer additive:
Project Polysaccharide Lalgine Sulfate radical
Content % 65.2% 30.1% 30.4%
Ultrafiltration waste liquid is obtained two complete micro-foliage fertilizer of algae after reverse osmosis membrane is concentrated.Detect through atomic absorption spectrophotometer, the content recording 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 be obtained 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 DEG C, stir 1.5 hours, add 2Kg polysaccharide degrading enzyme, adjustment system PH is 6.0, be warming up to 50 DEG C, continue stirring 1 hour, obtain two marine alga enzymolysis solutions and two marine alga slag through centrifugation while hot.
3, the preparation of two marine alga fertilizer
Two marine alga enzymolysis solution is through high-performance liquid chromatogram determination, and two Sargassum polysaccharides occurs 5 fragments altogether between molecular weight 150,000-30 ten thousand, therefore select molecular weight be 100,000 ultra-filtration membrane carry out ultrafiltration and concentration, finally obtain two Sargassum polysaccharides extracting solution.Detect through Phenol sulfuric acid procedure, the two polysaccharides content in two Sargassum polysaccharides extracting solution are 18.26%.This extracting solution, through lyophilize, prepares two Sargassum polysaccharides powdered fertilizer additive, can be used for the interpolation of various marine alga fertilizer.Result is as follows after testing for two Sargassum polysaccharides powdered fertilizer additive:
Project Polysaccharide Lalgine Sulfate radical
Content % 45.2% 15.6% 28.6%
Ultrafiltration waste liquid is obtained two complete micro-foliage fertilizer of algae after reverse osmosis membrane is concentrated.Detect through atomic absorption spectrophotometer, the content recording 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 only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still can modify to the technical scheme described in previous embodiment, or equivalent replacement is carried out to wherein portion of techniques feature; And these amendments 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.

Claims (8)

1. a preparation method for two marine alga fertilizer, is characterized in that it comprises the following steps:
1) pre-treatment of two marine alga: 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; After fresh brown alga drains surface-moisture, be 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, obtained green alga is stuck with paste and brown alga is stuck with paste;
After described freeze thawing all adopts-4 DEG C of cold house's precoolings ,-30 DEG C after cold house quick freezing 5-6 hour, after freezing, with steam thawing;
2) extraction of two Sargassum polysaccharides:
Two marine alga coordinated enzymatic hydrolysis: get described fresh green alga after freeze thawing and brown alga, or get the described green alga after freeze thawing and to stick with paste and brown alga is stuck with paste, be that 1:2-2:1 is dropped into reactor according to the mass ratio of green alga and brown alga, add the water accounting for marine alga quality 10-15 times;
Add the prozyme accounting for marine alga total mass 2%-3% again, regulatory enzyme enzymatic hydrolysis system pH is 3.5-4.5, enzymatic hydrolysis system temperature is kept to be 40-55 DEG C, enzymolysis 1.5-2 hour, after add the polysaccharide degrading enzyme accounting for marine alga total mass 1-2%, adjustment system pH is 5.5-6.5, carries out selective degradation to two Sargassum polysaccharides, 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;
Described prozyme is selected from one or more in cellulase, proteolytic enzyme, polygalacturonase, and total enzyme work of prozyme is 3 × 10 4-8 × 10 4iU;
3) preparation of marine alga fertilizer
Two marine alga slags after enzymolysis, after drying granulation, prepare two marine alga organic granular fertilizer; Two marine alga enzymolysis solutions after centrifugal, getting molecular weight is 10,000-10 ten thousand daltonian pairs of Sargassum polysaccharides, carries out ultrafiltration, prepares two Sargassum polysaccharides concentrated solution, obtained two Sargassum polysaccharides fertilizer additive after lyophilize.
2. the preparation method of according to claim 1 pair of marine alga fertilizer, is characterized in that, 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.
3. the preparation method of according to claim 1 pair of marine alga fertilizer, is characterized in that, in described step 3), bake out temperature remains on 80-95 DEG C, and through shear granulation, control particle diameter is 2-3mm.
4. the preparation method of according to claim 1 pair of marine alga fertilizer, is characterized in that, the waste liquid in described step 3) after ultrafiltration prepares two complete micro-foliage fertilizer of marine alga after reverse osmosis membrane is concentrated.
5. the preparation method of according to claim 1 pair of marine alga fertilizer, it is characterized in that, the pretreated method of fresh green alga described in described step 1) is: the fresh green alga extrusion dehydration baling equipment just salvaging disembarkation is carried out extrusion dehydration, first slough the free-water of 20-30%, water content is down to 60-70%, and volume-diminished is original 1/4-1/5; With shears, green alga is broken, the free-water in releasing structure, then carries out secondary extrusion dehydration, makes water content be down to 50%-60%.
6. the preparation method of according to claim 1 pair of marine alga fertilizer, is characterized in that, the dry green alga in described step 1) and the water content of dry brown alga are less than 10%, pulverizes, and crosses 60 order-100 mesh sieves and obtains chlorella powder and brown alga powder.
7. two marine alga fertilizers that the preparation method according to any one of claim 1-6 obtains.
8. according to claim 7 pair of marine alga fertilizer, is characterized in that, described pair of marine alga fertilizer specifically comprises the two algae complex polysaccharide fertilizer additives utilizing two marine alga coordinated enzymatic hydrolysis to prepare; Utilize two marine alga organic granular fertilizers prepared by two marine alga slag; Utilize two Trace Elements In Seaweeds foliage fertilizers prepared by two marine alga complex polysaccharide extraction waste liquid.
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