CN103319286A - Urea formaldehyde compound fertilizer containing chelating medium/trace element and preparation method thereof - Google Patents
Urea formaldehyde compound fertilizer containing chelating medium/trace element and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a urea formaldehyde compound fertilizer containing a chelating medium/trace element and a preparation method thereof. The urea formaldehyde compound fertilizer comprises the following raw materials in parts by weight: 0.2-0.4 part of medium trace element chelating liquid, 4.5-5.5 parts of urea formaldehyde, 1.5-3.0 parts of monoammonium phosphate, 1.5-3.0 parts of potassium sulphate, 0.5-1.5 part of auxiliary material and 0.06-0.1 part of coated material. A slow-dissolving organic nitrogenous fertilizer synthetic process is effectively combined with a coated technology so as to realize the slow release and long-acting function of nitrogen, the balanced fertilization is paid attention to by taking the high efficiency, the environmental protection and the greenization as the aim, the utilization rate of the fertilizer is increased through the balanced application of nutrients, the release and the utilization of the fertilizer are completed through the combination of the fertilizer and soil, the medium trace element is supplemented while the requirements of crops in different growing periods on the nutrients are satisfied, and the occurrence of the nutrient deficiency symptoms of the crops is effectively avoided. The used materials are non-toxic, harmless, safe and environment-friendly in use.
Description
Technical field
The present invention relates to biological technical field, be specifically related to a kind of urea formaldehyde compound manure that contains trace element in the chelating attitude and preparation method thereof.
Background technology
In recent years, fertilizer consumption rises year by year.But owing to utilizing unreasonable, cause chemical fertilizer utilization ratio lower, the this season utilization ratio of nitrogenous fertilizer only has 20%-35%, phosphorus is 10%～20%, potassium is 30%～35%, not only caused direct financial loss, and some areas because improper fertilization has caused environmental pollution the problems such as nitrate nitrogen content exceeds standard in earth's surface eutrophication, underground water and the vegetables, the increase of nitrous oxide emission amount appear.The serious imbalance of soil fertility is being slowed down the volume increase of grain, peasant's phenomenon that Higher output is not accompanied by a higher income occurs.
In biological fertilizer field, described middle trace element comprises moderate-element and trace element, and wherein moderate-element is some thousandths of at the plant materials intensive amount, comprises calcium, magnesium, sulphur; Trace element is ten thousand at the plant materials intensive amount/several below, comprise iron, copper, zinc, manganese, molybdenum, boron, although middle trace element content is lower, very large to the effect of plant.
The middle trace element particularly deficient phenomenon of trace element is on the rise in China, and China's boron deficiency area lacks the zinc area more than 20% more than 40%, and manganese deficiency, iron deficiency, scarce copper face amass and be respectively about 10%, 5%, 1%.The fertilizer efficiency that studies show that in the chelating attitude trace element normally inorganic middle trace element 2-5 doubly, wherein the fertilizer efficiency of chelating attitude zinc can reach 10 times of inorganic zinc.Therefore but the unit cost of trace element take generally highly than inorganic middle trace element in the chelating, produces that trace element will be significant to raising crop yield and quality in the chelating attitude cheap and easy to get.
In China, the research that middle trace element is combined with slow release fertilizer has been reported, but it is rarely seen that middle trace element is carried out after the chelating research of being combined with the slow release fertilizer such as urea formaldehyde again.Therefore, explore a kind of nitrogenous fertilizer of can controlling and discharge speed, satisfy again the comprehensive fertilizer of crop alimentary and have realistic meaning.
Summary of the invention
The purpose of this invention is to provide a kind of urea formaldehyde compound manure that contains trace element in the chelating attitude.
Another purpose of the present invention provides the preparation method of above-mentioned compound manure.
In order to achieve the above object, the present invention adopts following technical scheme.
A kind of urea formaldehyde compound manure that contains in the chelating attitude trace element is that the raw material by following weight part makes: in trace element chelated liquid 0.2-0.4 part, urea formaldehyde 4.5-5.5 part, monoammonium phosphate 1.5-3.0 part, vitriolate of tartar 1.5-3.0 part, auxiliary material 0.5-1.5 part, coated fertilizer 0.06-0.1 part.
The concentration of trace element chelated liquid is 0.04-0.06kg/L in described.The moderate-element of trace element chelated liquid wherein (calcium and magnesium sum) concentration sum is 0.03-0.05kg/L, and trace element (copper, iron, manganese, zinc, boron, molybdenum sum) concentration sum is 0.008-0.015kg/L.
Described auxiliary material is understood by one of ordinary skill in the art any commercially available and be of value to the auxiliary material of plant-growth, such as clay, plant ash or concrete fertilizer etc.
Described compound manure is preferably made by the raw material of following weight part: in 0.3 part of trace element chelated liquid, 5 parts of urea formaldehydes, 2 parts of monoammonium phosphates, 2 parts of vitriolate of tartar, 0.6 part of auxiliary material, 0.1 part of coated fertilizer.
Described coated fertilizer is selected from a kind of in chitosan, xylogen and the diatomite.
The above-mentioned preparation method who contains the compound manure of trace element in the chelating attitude; may further comprise the steps: will be delivered in the tablets press after urea formaldehyde and monoammonium phosphate, vitriolate of tartar, the auxiliary materials and mixing; trace element chelated liquid during granulation is sprayed simultaneously; after drying, the cooling mixture is delivered in the coating machine; spray coated fertilizer, must contain the urea formaldehyde compound manure of trace element in the chelating attitude.Wherein, each proportioning raw materials is: in trace element chelated liquid 0.2-0.4 part, urea formaldehyde 4.5-5.5 part, monoammonium phosphate 1.5-3.0 part, vitriolate of tartar 1.5-3.0 part, auxiliary material 0.5-1.5 part, coated fertilizer 0.06-0.1 part.
Trace element chelated liquid is made by following steps in described:
1) will mix with sodium nitrate solution behind the full water-soluble biochemical fulvic acid wiring solution-forming, the inorganic salt of trace element in adding again, constant temperature stirs and carries out chelatropic reaction; Xanthohumic acid content 〉=50.0% in the described biochemical fulvic acid, the pH value is between 5.0-6.0.
The inorganic salt of described middle trace element comprise the inorganic salt of moderate-element: the inorganic salt of nitrocalcite, sal epsom and trace element: borax, zinc sulfate, manganous sulfate, ferrous sulfate, copper sulfate, ammonium molybdate.
2) step 1) gained chelating liquid is mixed with aminoacids solution, constant temperature stirs and carries out chelatropic reaction, trace element chelated liquid in obtaining.
Wherein, trace element chelated liquid is made by following steps in described:
Described step 1) is specially: it is 30-40% solution that the full water-soluble biochemical fulvic acid is prepared weight ratio, be that the sodium nitrate solution of 1mol/L mixes according to volume ratio 5:1 and concentration, the inorganic salt of trace element in adding again, make the concentration of middle trace element maintain 0.048-0.075kg/L, the condition that keeps 40-60 ℃ of constant temperature, chelatropic reaction 48-60h is carried out in stirring, and mixing speed is 20r/min.
Wherein the mass ratio of moderate-element and trace element is (4-5) in the inorganic salt of middle trace element: 1.
Described step 2) is specially: step 1) gained chelating liquid is mixed with aminoacids solution according to volume ratio 5:1, keep constant temperature 40-60 ℃ condition, chelatropic reaction 24-36h is carried out in stirring, mixing speed is 20r/min, trace element chelated liquid in obtaining, wherein the concentration of trace element is 0.04-0.06kg/L.
Technique effect of the present invention: the present invention will delay and be dissolved with machine nitrogenous fertilizer synthesis technique and the effective combination of film-coating technique, and then realization nitrogen slowly-releasing and long-acting function, simultaneously take efficient, environmental protection, green as aim, pay attention to balance fertilizing, balancedly use to increase operation rate by nutrient, be combined release and the utilization of finishing fertilizer with edaphic condition two aspects from fertilizer itself, when satisfying crop different growing stages nutrient demand, trace element effectively prevents the generation of crop nutritional deficiency disease in replenishing.Selected material is all nontoxic, harmless, uses safety and environmental protection.
Description of drawings
Fig. 1 is preparation method's schema of trace element in the chelating attitude.
Fig. 2 is the preparation method's schema that contains the urea formaldehyde compound manure of trace element in the chelating attitude.
Fig. 3 is the nitrogen releasing curve diagram of different fertilizer.
Fig. 4 is the sickness rate figure of tomato under the different fertilizer effect.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
(1) preparation of trace element chelated liquid in:
As shown in Figure 1, select the complete water-soluble biochemical fulvic acid 30kg(xanthohumic acid content of high-quality 〉=50.0%, pH value 5.5), the water that adds 70L dissolves, after the sodium nitrate solution 10L that gets biochemical fulvic acid solution 50L and concentration and be 1mol/L mixes, add 10kg nitrocalcite, the 5kg magnesium sulfate heptahydrate, the 1kg borax, 0.7kg Zinc Sulphate Heptahydrate, 0.5kg manganous sulfate, 0.4kg ferrous sulfate, 0.3kg cupric sulfate pentahydrate and 0.2kg ammonium molybdate, the condition that keeps 50 ℃ of constant temperature, stir with rotating speed 20r/min, carry out a chelatropic reaction of middle trace element, the reaction times is controlled at 55h, obtains chelating liquid one time;
First mass percent 35% aminoacids solution being carried out removal of impurities processes, guarantee that its stability constant is moderate, get the above-mentioned chelating liquid of 50L and the aminoacids solution 10L mix and blend of handling well, the condition that keeps 50 ℃ of constant temperature, control mixing speed 20r/min, carry out the secondary chelatropic reaction of middle trace element, the reaction times is 30h, (moderate-element content is: 0.04kg/L, micronutrient levels is trace element chelated liquid in obtaining: 0.01kg/L).
(2) preparation of urea formaldehyde:
In reactor, add 500L water, be warming up to 65 ℃, add 500kg urea, with mass percent 20%NaOH adjust pH to 8.6, add 312.5kg formaldehyde after the stirring and dissolving, treat that temperature rises to 85 ℃, constant temperature 36min when being cooled to 30 ℃, dehydrates to get urea formaldehyde.
(3) contain in the chelating attitude preparation of the urea formaldehyde compound manure of trace element
As shown in Figure 2; step (2) gained urea formaldehyde 500kg is dropped into hopper with 200kg monoammonium phosphate, 200kg vitriolate of tartar, 60kg clay; be delivered to rotary drum granulator behind the mixing, mass flow is controlled at 200kg/min, continuously convey materials; the tablets press rotating speed is controlled at 12r/min; continuous granulation sprays trace element chelated liquid in step (1) gained, sprinkling amount 30kg simultaneously; spray rate 3kg/min sprays continuously.
In the time of granulation, trace element chelated liquid and material organically combine in making, again after drying, the cooling, with mass transport to coating machine, spray chitosan and carry out coating, sprinkling amount 10kg, spray rate is controlled at 1.5kg/min, finally obtain containing the urea formaldehyde compound manure of trace element in the chelating attitude, then will sieve qualified product and pack.Products obtained therefrom nitrogen content 19%.
(1) preparation of trace element chelated liquid in:
As shown in Figure 1, select the complete water-soluble biochemical fulvic acid 30kg(xanthohumic acid content of high-quality 〉=50.0%, pH value 5.5), the water that adds 70L dissolves, after the sodium nitrate solution of getting biochemical fulvic acid solution 50L and 10L concentration and be 1mol/L mixes, add 9kg nitrocalcite, the 4kg magnesium sulfate heptahydrate, 1.3kg borax, 0.5kg Zinc Sulphate Heptahydrate, 0.5kg manganous sulfate, 0.4kg ferrous sulfate, 0.3kg cupric sulfate pentahydrate and 0.2kg ammonium molybdate, the condition that keeps 50 ℃ of constant temperature, stir with rotating speed 20r/min, carry out a chelatropic reaction of middle trace element, the reaction times is controlled at 55h, obtains chelating liquid one time;
First mass percent 35% aminoacids solution being carried out removal of impurities processes, guarantee that its stability constant is moderate, get the aminoacids solution mix and blend that the above-mentioned chelating liquid of 50L and 10L handle well, the condition that keeps 40 ℃ of constant temperature, control mixing speed 20r/min, carry out the secondary chelatropic reaction of middle trace element, the reaction times is 30h, and (moderate-element content is 0.036kg/L: micronutrient levels is trace element chelated liquid in obtaining: 0.01kg/L).
(2) preparation of urea formaldehyde:
In reactor, add 100L water, be warming up to 65 ℃, add 400Kg urea, with mass percent 20%NaOH adjust pH to 8.6, add 285kg formaldehyde after the stirring and dissolving, treat that temperature rises to 90 ℃, constant temperature 30min when being cooled to 30 ℃, dehydrates to get urea formaldehyde.
(3) contain in the chelating attitude preparation of the urea formaldehyde compound manure of trace element
As shown in Figure 2; step (2) gained urea formaldehyde 500kg is dropped into hopper with 200kg monoammonium phosphate, 200kg vitriolate of tartar, 50kg concrete fertilizer; be delivered to rotary drum granulator behind the mixing, mass flow is controlled at 200kg/min, continuously convey materials; the tablets press rotating speed is controlled at 11r/min; continuous granulation sprays trace element chelated liquid in step (1) gained, sprinkling amount 40.0kg simultaneously; spray rate 3.5kg/min sprays continuously.In the time of granulation, middle trace element and material are organically combined, after drying, the cooling, mass transport to coating machine, is sprayed shell diatomite and carried out coating again, sprinkling amount 10.0kg, spray rate is controlled at 1.5kg/min, continuously coating.Finally obtain containing the urea formaldehyde compound manure of trace element in the chelating attitude, then will sieve qualified product and pack.Products obtained therefrom nitrogen content 18%.
Test example 1
Utilize water seaoning that embodiment 1 is carried out the nitrogen release test.
Take by weighing embodiment 1(nitrogen content 19%), embodiment 2(nitrogen content 18%), urea formaldehyde (nitrogen content 38%) and common each 100g of large grain urea (nitrogen content 46%), place respectively nylon net bag, immersion fills in the container of 200mL deionized water again, cultivates in 25 ℃ of thermostat containers.Take out the leach liquor in 3 containers during respectively at the 1st, 2,5,7,10,15,20,28,35,45,50 and 100 day, again add again the 200mL deionized water after taking out each time leach liquor, continue to soak sample.Adopt CO (NH in the each leach liquor of paradimethy laminobenzaldehyde-spectrophotometry
2)
2-N content.
As shown in Figure 3, common large grain urea first half of the month substantially linearly discharges, afterwards a little mitigation, but release rate still is higher than slow-release carbamide far away, and at 15 days left and right sides release rates up to 80%; A quick release period all appearred in urea formaldehyde and embodiment 1, embodiment 2 at front 10 days, be tending towards afterwards relaxing, after 40 days, the rate of release of embodiment 1, embodiment 2 is lower than the rate of release of urea formaldehyde, the nitrogen of residue 30% can continue later at 100 days to discharge, satisfy the nutrient demand in crop later stage, and the nitrogen that urea formaldehyde only remains less than 20% discharged later at 100 days.
Test example 2
The potted plant fertilizer efficiency experiment of paddy rice
It is that the plastic tub of 25cm is carried paddy rice that high 30cm, diameter are adopted in test, totally 3 basins, every basin dress 10kg soil.Take by weighing respectively first phosphate fertilizer, each 3g of potash fertilizer evenly is mixed in every basin soil, taking by weighing common large grain urea, urea formaldehyde, 1 three kinds of each 3g of nitrogenous fertilizer of embodiment, to impose on respectively the degree of depth be in 8cm and the 16cm soil again, and according to every basin three caves, the quantity that every cave is three is transplanted, water routine observation after the final singling.
Observations: growth does not have too big difference to every basin paddy rice in tillering phase, but after the jointing stage, the paddy rice growing way of common large grain Urea treatment group is obviously relatively poor, reason is that urea release is too fast, can't satisfy the growth of later stage paddy rice, urea formaldehyde and embodiment 1 separately the paddy rice for the treatment of group in jointing stage, boot stage and early stage milk stage, growth situation basic simlarity, but in paddy rice later stage milk stage and full ripe stage, the paddy rice growing way of embodiment 1 treatment group obviously is better than the urea formaldehyde treatment group, illustrates that the slow release effect of embodiment 1 obviously is better than single urea formaldehyde product.Finally by survey producing, the rice yield of embodiment 1 fertilising exceeds 3% than the rice yield of urea formaldehyde treatment group, exceeds 8% than the output of common large grain Urea treatment group.By such scheme embodiment 2 is tested, test result is identical with embodiment 1.
Test example 3
Test is carried out in the experimental plot of Yantai City Shandong Baoyuan Biology Co., Ltd on-site, and the experiment crop is tomato, and sample plot soil is umber, new soil, unmatched stubble crop.Test fertilizer be embodiment 1 and embodiment 2, documents (
98103120.X) described fertilizer and reference examples (not applying fertilizer).Every kind of fertilizer divides three residential quarters to carry out, and each residential quarter area is 100m
2
Early stage, soil base manure all adopted nitrogen: phosphorus: the Chemical Mixed Fertilizer (Shandong Baoyuan Biology Co., Ltd) of potassium=16-5-20 proportioning, rate of fertilizer application is 100kg/ mu.Tomato is transplanted seedlings after the field planting, uses respectively embodiment 1 fertilizer, embodiment 2 fertilizer, the described fertilizer of documents and contrast (not applying fertilizer) and topdresses, and rate of fertilizer application is 60kg/ mu, and the later stage is all adopted nitrogen: phosphorus: the macroelement punching fertilising of potassium=10-20-30.
Observations is as shown in Figure 4: the tomato of control treatment group, the sickness rate of nutritional deficiency disease is more than 35%, especially the sickness rate of bitter pit is more than 15%, the sickness rate of the described fertilizer bitter pit of documents is 8%, other sickness rate by the disease that nutritional deficiency causes is 4%, and the sickness rate of using the tomato bitter pit of embodiment 1 fertilizer and 2 fertilizer on average only is 4%, and the sickness rate of the disease that other nutritional deficiency causes also only is 1%.And tomato is large, and mass color is good, and mouthfeel is contrast and the described fertilizer treatment group of documents good also.Explanation, micro-successful is better than other products in embodiment 1 fertilizer and the embodiment 2 fertile additional crops, reason mainly is that embodiment 1 and embodiment 2 fertile centering trace elements have carried out biochemical fulvic acid and amino acid whose double sequestration, inorganic salt than trace element in simple easily absorb, and specific absorption is high.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. one kind contains urea formaldehyde compound manure micro-in the chelating attitude, it is characterized in that, described compound manure is made by the raw material of following weight part: in trace element chelated liquid 0.2-0.4 part, urea formaldehyde 4.5-5.5 part, monoammonium phosphate 1.5-3.0 part, vitriolate of tartar 1.5-3.0 part, auxiliary material 0.5-1.5 part, coated fertilizer 0.06-0.1 part.
2. compound manure according to claim 1 is characterized in that, described in the concentration of trace element chelated liquid be 0.04-0.06kg/L.
3. compound manure according to claim 1 is characterized in that, described compound manure is made by the raw material of following weight part: in 0.3 part of trace element chelated liquid, 5 parts of urea formaldehydes, 2 parts of monoammonium phosphates, 2 parts of vitriolate of tartar, 0.6 part of auxiliary material, 0.1 part of coated fertilizer.
4. compound manure according to claim 1 is characterized in that, described coated fertilizer is selected from a kind of in chitosan, xylogen and the diatomite.
5. the preparation method of the arbitrary described compound manure of claim 1-4; it is characterized in that; may further comprise the steps: will be delivered in the tablets press after urea formaldehyde and monoammonium phosphate, vitriolate of tartar, the auxiliary materials and mixing; trace element chelated liquid during granulation is sprayed simultaneously; after drying, the cooling mixture is delivered in the coating machine; spray coated fertilizer, must contain the urea formaldehyde compound manure of trace element in the chelating attitude.
6. preparation method according to claim 5 is characterized in that, described in trace element chelated liquid made by following steps:
1) will mix with sodium nitrate solution behind the full water-soluble biochemical fulvic acid wiring solution-forming, the inorganic salt of trace element in adding again, constant temperature stirs and carries out chelatropic reaction one time;
2) step 1) gained chelating liquid is mixed with aminoacids solution, constant temperature stirs and carries out chelatropic reaction, trace element chelated liquid in obtaining.
7. preparation method according to claim 6, it is characterized in that, described step 1) is specially: it is 30-40% solution that the full water-soluble biochemical fulvic acid is prepared weight ratio, be that the sodium nitrate solution of 1mol/L mixes according to volume ratio 5:1 and concentration, the inorganic salt of trace element make the concentration of middle trace element maintain 0.048-0.075kg/L in adding again, the condition that keeps 40-60 ℃ of constant temperature, chelating is carried out in stirring one time, reaction 48-60h, and mixing speed is 20r/min.
8. preparation method according to claim 7 is characterized in that, the moderate-element in the inorganic salt of described middle trace element is (4-5) with the mass ratio of trace element: 1.
9. preparation method according to claim 6, it is characterized in that, described step 2) is specially: step 1) gained chelating liquid is mixed with aminoacids solution according to volume ratio 5:1, keep constant temperature 40-60 ℃ condition, secondary chelatropic reaction 24-36h is carried out in stirring, mixing speed is 20r/min, trace element chelated liquid in obtaining, and wherein the concentration of trace element is at 0.04-0.06kg/L.
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