CN103819276A - Slow-release seaweed fertilizer with high water-retaining property and preparation method thereof - Google Patents
Slow-release seaweed fertilizer with high water-retaining property and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a slow-release seaweed fertilizer with a high water-retaining property and a preparation method thereof. The slow-release seaweed fertilizer with the high water-retaining property comprises components in parts by weight as follows: 2-200 parts of a cross-linking agent, 3-200 parts of an initiating agent, 1-100 parts of carrageenan, 2-800 parts of acrylic acid, 10-900 parts of diatomaceous earth and 40-300 parts of specific fertilizer source. According to the slow-release seaweed fertilizer with the high water-retaining property, the surface of super absorbent resin on the outer layer is rough and porous, and the surface of carrageenan gel matrix on the inner layer is flat and compact, so that a water holding capacity and a water-retaining rate of soil can be increased, the evaporation of water is reduced, the irrigation cycle of the soil is prolonged, and the utilization rate of water is increased; and meanwhile, the soil is prevented from hardening, a good slow-release property and high compressive strength are achieved, and production, transportation and practical use of the fertilizer are facilitated.
Description
Technical field
The present invention relates to crop fertiliser production Application Areas, more specifically point out, the present invention relates to a kind of high-moisture-retention slowly-releasing marine alga fertilizer and preparation method thereof.
Background technology
The Sustainable development of agricultural is the basis of human society, sustainable economic development.China has a large population in a small area, and the limited amount of per capita land resources, particularly cultivated land resource will be resolved food problem, just must improve the output on unit soil.Fertilising for increases in grain production, get agricultural profit and the aspect such as preservation of fertility has played active effect, it has been recognized that soil fertility keeps the importance to crop yield.Soil nutrient is the most important basic substance of soil fertility, and fertilizer is the main source of soil nutrient, thereby is also one of important substance basis of agricultural sustainable development.From 1977 to 2005, China every year consumption of synthetic nitrogenous fertilizer is increased to 2,621 ten thousand tons from 7,070,000 tons, but compare with the utilization rate of nitrogen fertilizer of developed country 45%, the utilization ratio of China's farmland nitrogenous fertilizer is only 30% ~ 35%, low utilization rate of nitrogen fertilizer causes serious problem of environmental pollution, as soil acidification, body eutrophication and greenhouse gas emission etc.In the face of population, grain, resource, Environment and energy Five problems, the Sustainable development of agricultural is subject to paying attention to more and more widely, and exploitation slow release fertilizer is the effective way that improves utilization rate of fertilizer.In numerous nitrogenous fertilizer, urea is because it is used with relative low production cost on a large scale compared with high nitrogen content.The slow release product of urea is generally divided into two classes: (1) urea and aldehyde compound generation condensation reaction, obtain urea aldehydes condensation slow release fertilizer; (2) urea granules is carried out to polymer capsule processing.Wherein, polymer science and technology had obtained very great development in recent years, can be designed to fertilizer to carry out the film material of controllable release, and therefore, the slow-release nitrogen fertilizer of polymer capsule has good development prospect.Along with the scarcity day by day of petroleum resources and the continuous enhancing of people's environmental consciousness, utilizing reproducible natural resource to prepare environmentally friendly coated fertilizer has been one of important topic of current research.Vegetable polysaccharides is because its wide material sources, recyclability, nontoxic inexpensive and biological degradability are prepared to multiple matrix type composite material.
Carrageenin claims again carrageenin, carrageeman, is the lyophilic colloid being present in some red algaes, can from the red algaes such as Eucheuma muricatum (Gmel.) Web． Van Bos．, extract, and is a kind of Linear Polymer polysaccharide that has Important Economic to be worth.The red algae kind that contains carrageenin basic structure nearly more than 80 is planted, and type and quantity that different marine alga kinds contains carrageenin are different.The carrageenin in different red algaes source has different fine structures, and its colloidal property is not identical yet; Even same source, different technique extraction conditions cause different molecular weight degradations, and product property is also discrepant, and therefore carrageenin is the title of a broad sense.Various carrageenins are all linear polysaccharides that α-D-galactose unit of the β-D-semi-lactosi and the Isosorbide-5-Nitrae that are connected by 1,3--be connected is alternately formed by connecting.Wherein 1,3-connects unit and occurs with 2-and 4-sulfuric ester form, also may not exist; Isosorbide-5-Nitrae-connection unit occurs with 2-and 6-sulfuric ester form, or with 2,6-di-sulfate, or occur with forms such as 3,6-Anhydrogalactose bases.On basic polymkeric substance, substituent multiple possibility makes the diversification of forms of carrageenin, but they can regard the mutation of several desirable representative polysaccharide as, the carrageenin of having named has Kappa, Lambda, Iota, Mu, Nu, Theta, Xi type carrageenin etc.Carrageenin gel matrix is used widely in drug delivery system and special packet mould material, but there is not yet report as coated fertilizer in agricultural.
Obtain a kind of All Pure Nature gel matrix of ionomer by dripping carrageenin solution in the mixed aqueous solution to calcium chloride and Repone K, can improve like this physical strength of carrageenin gel and reduce its fragility.Except fertilizer, water is the important factor of another restriction agricultural development, and China is one of country that lack of water is the most serious in the world, and lack of water is considered to the chief threat of grain long-term safety.Diatom in diatomite has many different shapes, and as discoid, needle-like, tubular, pinniform etc., aerated density is 0.3 ~ 0.5g/cm
3, Mohs' hardness is that 1 ~ 1.5(diatom bone particulate is 4.5 ~ 5mm), porosity reaches 80 ~ 90%, can absorb the water of 1.5 ~ 4 times of itself weight.Super absorbent resin is a kind of hydrophilic high molecular material, and it can absorb the even water of several thousand times of self hundred times, form water insoluble but can be at the swelling tridimensional network of water camber, even still there is good water absorbing and retaining properties adding to depress.Due to its unique water absorbing and retaining properties, super absorbent resin is widely applied in agroforestry, and it can improve Soil structure, reduces the watering period and improve efficiency of water application etc.
Summary of the invention
In order to utilize the feature of above-mentioned current material, and expand its Application Areas, the invention discloses a kind of high-moisture-retention slowly-releasing marine alga fertilizer and preparation method thereof.
Prepare a kind of water-maintaining slowly-releasing nitrogenous fertilizer of double-deck coating.Its kernel is source of manure particle, and internal layer coated fertilizer is carrageenin gel matrix, and outer coated fertilizer is carrageenin grafted polyacrylic acid/diatomite super absorbent resin.First, super absorbent resin is used as outer coated fertilizer, and this process has also reduced the loss of fertilizer in maintaining super absorbent resin water-absorbing-retaining function.Secondly, carrageenin gel matrix is introduced in the preparation of slow release fertilizer, can reduce the biodegradability of production cost and the raising product of product.In addition, we wish that this coated fertilizer can delay the release of nitrogen, improve the consumption of soil moisture and minimizing irrigation water etc.
The technical solution adopted in the present invention is: by weight, and 2 ~ 200 parts of a kind of high-moisture-retention slowly-releasing marine alga fertilizer dosage of crosslinking agent, 3 ~ 200 parts of initiator amounts, 1 ~ 100 part of carrageenin consumption, 2 ~ 800 parts of vinylformic acid consumptions, 10 ~ 900 parts of diatomite consumptions, 40 ~ 300 parts of specific source of manure consumptions.
Described linking agent is glycidyl methacrylate, N, wherein a kind of of N '-methylene-bisacrylamide, Vinylstyrene, vulcabond or the wherein multiple mixture of weight ratio arbitrarily.
Described initiator is a kind of or multiple mixture of weight ratio arbitrarily wherein of Potassium Persulphate, Sodium Persulfate, ammonium persulphate.
Described carrageenin is a kind of of Kappa, Lambda, Iota, Mu, Nu, Theta, Xi type carrageenin or the multiple mixture of weight ratio arbitrarily wherein.
The described source of manure can be nitrogenous fertilizer, phosphate fertilizer, potash fertilizer and composite fertilizer, as urea, dipotassium hydrogen phosphate, ammonium chloride etc.
A kind of high-moisture-retention slowly-releasing marine alga fertilizer, concrete preparation comprises the following steps:
(1) preparation of carrageenin grafted polyacrylic acid/diatomite super absorbent resin
Under nitrogen protection, carrageenin and water are dissolved 30 minutes by a certain percentage in reactor to 80 ℃ of water temperatures.After carrageenin is dissolved into homogeneous transparent solution completely, be cooled to 60 ℃, add a certain amount of vinylformic acid, N, N '-methylene-bisacrylamide and diatomite powder, stir 10 minutes, then certain density ammonium persulfate aqueous solution is added to initiated polymerization in reactor.This polyreaction continues to stop after 3 hours at 80 ℃, after product drying, pulverizing, mistake 100 ~ 200 eye mesh screens, stores for future use.
(2) preparation of carrageenin gel matrix
Carrageenin is dissolved in distilled water, being prepared into carrageenin concentration is 1%(w/v) solution, this polysaccharide soln extruding is dropped to calcium chloride (3% is housed, and Repone K (3% w/v), w/v) in the reactor of mixing solutions, stir, this polysaccharide mixing solutions forms transparent gel matrix under the effect of ionomer, and this gel matrix was kept after 30 minutes in salts solution.
(3) preparation of slow release fertilizer
First, be that source of manure particle within the scope of 2.0 ~ 2.5mm is placed in disk by particle diameter, rotary disk under the effect of atomized water, is wrapped in carrageenin gel matrix on particle as inner investment material.Subsequently, the transfer of granules to 40 ℃ of having wrapped up one deck carrageenin gel matrix is supplied, in case, after oven dry, to repeat operation above until reach certain internal layer membrane wrapping thickness.Finally, 100 ~ 200 order carrageenin grafted polyacrylic acid/diatomite super absorbent resin powder are put into disk, and rotary disk, makes super absorbent resin be wrapped on particle as peplos material, thereby obtain the double-contracting film fertiliser granulates of surface uniform densification, and in 40 ℃ of baking ovens dry for standby.
Compared with prior art, the invention has the beneficial effects as follows:
(1) outer super absorbent resin surface irregularity and porous, the gel matrix surfacing of internal layer carrageenin and densification;
(2) the water-absorbing-retaining experiment of coated fertilizer in soil shows, adds a small amount of coated fertilizer just can increase water holdup and the water retention of soil, falls low-moisture evaporation, extends the watering period of soil, improves the utilization ratio of moisture, can keep soil from packing together simultaneously;
(4) source of manure release rate that fertilizer was placed into the soil after 25 days is 94%, illustrates that it has good slow-releasing;
(5) carrageenin gel matrix is biodegradable coated fertilizer, is applied in agricultural, contributes to alleviate the problem of environmental pollution owing to using non-degradable organic synthesis base polymer material to cause;
(6) after coating, the ultimate compression strength of fertiliser granulates has improved 10%, is conducive to production and transport and actual use of fertilizer.
Accompanying drawing explanation
Fig. 1 is high-moisture-retention slowly-releasing marine alga fertilizer structural representation: (1) source of manure particle, (2) carrageenin gel coat, (3) carrageenin grafted polyacrylic acid/diatomite super absorbent resin layer;
Fig. 2 is the release rate time history plot of HFK001 nitrogen;
Fig. 3 is that different fertilizer is added the affect figure of rate of utilization on specific retesion of soil.
Embodiment
Below in conjunction with concrete embodiment, the present invention is described in further detail.Should understand embodiment below and only be not used in the restriction scope of the invention for the present invention is described.
embodiment 1
Prepare high-moisture-retention slowly-releasing marine alga fertilizer.
(1) preparation of carrageenin grafted polyacrylic acid/diatomite super absorbent resin
By weight, under nitrogen protection, carrageenin 5g and water 500g are dissolved 30 minutes in reactor to 80 ℃ of water temperatures.After carrageenin is dissolved into homogeneous transparent solution completely, be cooled to 60 ℃, add 7g vinylformic acid, 12g linking agent N, N '-methylene-bisacrylamide and 300g diatomite powder, stir 10 minutes.Then initiator 21g ammonium persulphate is added to initiated polymerization in reactor.This polyreaction continues to stop after 3 hours at 80 ℃, after product drying, pulverizing, mistake 80 eye mesh screens, stores for future use.
(2) preparation of carrageenin gel matrix
40g carrageenin is dissolved in 40L distilled water, and being prepared into carrageenin concentration is 1%(w/v) solution.This polysaccharide soln extruding is dropped in the reactor that 40L Repone K (3%, w/v) solution is housed, stir, this polysaccharide mixing solutions forms transparent gel matrix under the effect of ionomer, and this gel matrix was kept after 30 minutes in salts solution.
(3) preparation of slow release fertilizer
First, be that dipotassium hydrogen phosphate particle (source of manure) within the scope of 2.0 ~ 2.5mm is placed in disk by particle diameter, rotary disk under the effect of atomized water, is wrapped in carrageenin gel matrix on dipotassium hydrogen phosphate particle as inner investment material.Subsequently, the dipotassium hydrogen phosphate transfer of granules to 40 ℃ of having wrapped up one deck carrageenin gel matrix is supplied, in case, after oven dry, to repeat operation above until reach internal layer membrane wrapping thickness and be about 1mm.Finally, poly-80 order carrageenin grafting third coal acid/diatomite super absorbent resin powder is put into disk, rotary disk, super absorbent resin is wrapped on dipotassium hydrogen phosphate particle as peplos material, thereby obtain the double-contracting film dipotassium hydrogen phosphate particle of surface uniform densification, and in 40 ℃ of baking ovens dry for standby.
Obtain high-moisture-retention slowly-releasing marine alga fertilizer HFK001.
embodiment 2
Prepare high-moisture-retention slowly-releasing marine alga fertilizer.
(1) preparation of carrageenin grafted polyacrylic acid/diatomite super absorbent resin
By weight, under nitrogen protection, carrageenin 0.6kg and water 80kg are dissolved 30 minutes in reactor to 80 ℃ of water temperatures.After carrageenin is dissolved into homogeneous transparent solution completely, be cooled to 65 ℃, add 0.7kg vinylformic acid, 1.2kg linking agent Vinylstyrene and 60kg diatomite powder, stir 15 minutes.Then initiator 2.1kg Potassium Persulphate is added to initiated polymerization in reactor.This polyreaction continues to stop after 3 hours at 80 ℃, after product drying, pulverizing, mistake 100 eye mesh screens, stores for future use.
(2) preparation of carrageenin gel matrix
0.4kg carrageenin is dissolved in 400L distilled water, and being prepared into carrageenin concentration is 1%(w/v) solution.This polysaccharide soln extruding is dropped in the reactor that 400L Repone K (3%, w/v) solution is housed, stir, this polysaccharide mixing solutions forms transparent gel matrix under the effect of ionomer, and this gel matrix was kept after 30 minutes in salts solution.
(3) preparation of slow release fertilizer
First, be that urea granules (source of manure) within the scope of 2.0 ~ 2.5mm is placed in disk by particle diameter, rotary disk under the effect of atomized water, is wrapped in carrageenin gel matrix on urea granules as inner investment material.Subsequently, the urea granules that has wrapped up one deck carrageenin gel matrix is transferred to 40 ℃ in case, after oven dry, repeats operation above until reach internal layer membrane wrapping thickness and be about 1mm.Finally, 100 order carrageenin grafted polyacrylic acid/diatomite super absorbent resin powder are put into disk, and rotary disk, makes super absorbent resin be wrapped on urea granules as peplos material, thereby obtain the double-contracting film urea granules of surface uniform densification, and in 40 ℃ of baking ovens dry for standby.
Obtain high-moisture-retention slowly-releasing marine alga fertilizer HFN001.
embodiment 3
Get embodiment 2 high-moisture-retention slowly-releasing marine alga fertilizer HFN001 and measure its nitrogen release rate in soil.Fig. 2 is the release rate time history plot of high-moisture-retention slowly-releasing marine alga fertilizer HFK001 nitrogen in soil.As can be seen from the figure, be embedded in soil after the 2nd, 15 and 25 days, in coated fertilizer, the release rate of nitrogen is respectively 41%, 75% and 94%, and these data show that coated fertilizer has good slow-releasing in soil.First 5 days, nitrogen showed rate of release fast, and this is owing to the dissolving of kernel urea granules.After coated fertilizer is placed into the soil, its outer coating super absorbent resin can absorb the soil solution and the slow swelling hydrogel that becomes.The moisture that super absorbent resin absorbs slowly diffuses in fertilizer core, dissolved urea particle.Meanwhile, swelling due to gel, polymer three-dimensional network structure is expanded more, and it is large that micropore becomes, and makes this part dissolved nutrient can rapid diffusion, and enter in soil by coated fertilizer.After 5 days, the rate of release of nitrogen is obviously slack-off, and this is that in kernel, the concentration of nitrogen is more and more less because of the growth along with the time, and the inside and outside osmotic pressure of fertiliser granulates reduces, thereby has reduced the rate of release of nitrogen.In addition, a large amount of salt ions and soil small-particle are attracted in outer super absorbent resin coated fertilizer, and these particles have played to the release of nitrogen the effect that physics hinders.Meanwhile, due to the existence of these salt ions, the water-intake rate that makes super absorbent resin is than medium and small a lot of at tap water, be unfavorable for nitrogen to external diffusion, thereby nitrogen shows slow-releasing.And for the urea granules that does not do coating processing, it just can discharge self nitrogen of 98% in 12h.
embodiment 4
Get embodiment 2 high-moisture-retention slowly-releasing marine alga fertilizer HFN001 and measure its impact on specific retesion of soil.Great many of experiments shows, can reduce evaporation and the deep percolation of moisture to the super absorbent resin that adulterates in soil, and the moisture volume of holding of soil is increased.In water-deficient area, super absorbent resin can absorb large quantity of moisture and slowly emit moisture at period of drought between rainfall and during irrigation period, has extended the watering period, thereby has strengthened the drought-resistant ability of plant.Different fertilizer rate of application on the impact of specific retesion of soil as shown in Figure 3.As seen from the figure, the maximum water holdup that does not add the soil of coated fertilizer is 39%, and adds respectively after 1%, 2% and 3% coated fertilizer, and the maximum water holdup of soil is respectively 46.1%, 53.0% and 58.2%.Along with the increase of coated fertilizer rate of application, the amount of the super absorbent resin coated fertilizer wherein containing also increases, and therefore the water holdup of soil also increases gradually.Than control experiment (do not add fertiliser granulates in soil, other condition is identical), fertiliser granulates just can effectively improve the water holdup of soil under very little rate of application.Meanwhile, we also observe, and water is much slower than the speed of the soil by not adding fertiliser granulates by being added with the speed of soil of fertiliser granulates.Above experimental result shows, this fertiliser granulates has good water absorbing properties in soil, can obviously improve the moisture of soil and holds rate and reduce by oozing and reveal the moisture loss causing, is applied in agroforestry, effectively storing rainwater or irrigation water, thereby the utilization ratio of raising water resources.
embodiment 5
Get embodiment 2 high-moisture-retention slowly-releasing marine alga fertilizer HFN001 and measure its impact on soil water-retaining rate.Do not add the soil of fertiliser granulates, its water retention is 46%, dry after 10 days under state of nature, almost loses all moisture; And add respectively the soil of 1%, 2% and 3% fertiliser granulates, and its water retention is respectively 66%, 85% and 92%, dry after 10 days under state of nature, and its water retention is still 21%, 42% and 61%.As can be seen here, this coated fertilizer not only has good water-retaining capacity after adding soil, also has good water retention capacity simultaneously.This characteristic of fertiliser granulates mainly gives the credit to super absorbent resin and the diatomite coupling in its coated fertilizer, it can absorb stores a large amount of moisture, and slowly release stored moisture with the reduction of soil moisture, it is fully absorbed by crop, slow down the evaporation of soil moisture simultaneously, effectively improve the utilization ratio of water resources.Therefore, this tests prepared fertiliser granulates has good application prospect in arid, lack of water or the large area of daily evaporation amount.
Claims (8)
1. a high-moisture-retention slowly-releasing marine alga fertilizer, it is characterized in that: by weight, 2 ~ 200 parts of a kind of high-moisture-retention slowly-releasing marine alga fertilizer dosage of crosslinking agent, 3 ~ 200 parts of initiator amounts, 1 ~ 100 part of carrageenin consumption, 2 ~ 800 parts of vinylformic acid consumptions, 10 ~ 900 parts of diatomite consumptions, 40 ~ 300 parts of specific source of manure consumptions.
2. a kind of preparation method of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 1, concrete preparation comprises step: preparation, the preparation of carrageenin gel matrix and the preparation of slow release fertilizer of carrageenin grafted polyacrylic acid/diatomite super absorbent resin.
3. a kind of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 1, it is characterized in that: described linking agent is glycidyl methacrylate, N wherein a kind of of N '-methylene-bisacrylamide, Vinylstyrene, vulcabond or the wherein multiple mixture of weight ratio arbitrarily.
4. a kind of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 1, is characterized in that: described initiator is a kind of or multiple mixture of weight ratio arbitrarily wherein of Potassium Persulphate, Sodium Persulfate, ammonium persulphate.
5. a kind of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 1, is characterized in that: described carrageenin is a kind of of Kappa, Lambda, Iota, Mu, Nu, Theta, Xi type carrageenin or the multiple mixture of weight ratio arbitrarily wherein.
6. a kind of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 1, is characterized in that: the described source of manure can be for nitrogenous fertilizer, phosphate fertilizer, potash fertilizer and composite fertilizer, as urea, dipotassium hydrogen phosphate, ammonium chloride etc.
7. a kind of preparation method of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 2, it is characterized in that: in the preparation process of carrageenin grafted polyacrylic acid/diatomite super absorbent resin, under nitrogen protection, carrageenin is dissolved into after homogeneous transparent solution completely, be cooled to 40 ~ 60 ℃, add vinylformic acid, linking agent N, N '-methylene-bisacrylamide and diatomite powder, stir 1 ~ 60 minute, then initiator ammonium persulfate is added to initiated polymerization in reactor, this polyreaction continues to stop after 1 ~ 3 hour at 60 ~ 80 ℃, product drying, pulverize, after crossing screen cloth, store for future use.
8. a kind of preparation method of high-moisture-retention slowly-releasing marine alga fertilizer according to claim 2, it is characterized in that: in the preparation process of slow release fertilizer, source of manure particle is placed in to disk, rotary disk under the effect of atomized water, carrageenin gel matrix is wrapped on particle as inner investment material, subsequently, the transfer of granules of having wrapped up one deck carrageenin gel matrix is extremely supplied in case, after oven dry, repeat operation above until reach certain internal layer membrane wrapping thickness, finally, carrageenin grafted polyacrylic acid/diatomite super absorbent resin powder is put into disk, rotary disk, super absorbent resin is wrapped on particle as peplos material, thereby obtain the double-contracting film fertiliser granulates of surface uniform densification, and dry in baking oven.
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