Background technology
Water-soluble fertilizer is a kind of water-soluble polyelement composite fertilizer fully, and it can contain the needed whole nutritive elements of plant growth usually, like N, P, K macronutrient, and trace elements such as amount nutritive element and copper, iron, zinc, boron among Ca, Mg, the S.People can design the water-soluble fertilizer prescription according to the needed nutritional needs characteristics of plant growth fully, and its utilization rate of fertilizer almost is 2-3 a times of conventional composite chemical fertilizer.Secondly it can promptly be dissolved in the water, and is prone to absorbed by Crop High-efficient, and fertilizer efficiency is fast, and more crucial is that it can be applied to have the agricultural of spraying facilities such as drip irrigation, realizes that liquid manure is integrated, reaches the usefulness that water-saving is economized fertile saving of labor.Water-soluble fertilizer dips in root etc. with being used for fertigation, leaf dressing, soilless culture, seed soaking after water dissolution or the dilution usually, is to meet environmental protection more, the fertilizer of new generation of Sustainable development more, and also be that Chinese fertilizer industry and industry are given priority to problem and project.
At present, the main nutrient elements N of water-soluble fertilizer, P, K often derive from water-soluble products such as industrial grade monoammonium phosphate, PHOSPHORIC ACID TECH.GRADE potassium dihydrogen, Ureaphil, saltpetre.Though these water soluble fertilizer water-insolubles are lower, can realize that liquid manure is integrated well for dry or arid season crop provide macronutrient, liked by the peasant.But it is that raw material just can be produced the lower water-soluble fertilizer of water-insoluble that monoammonium phosphate, potassium primary phosphate, the Ureaphil composite fertilizer that contains the P element need adopt purifying phosphoric acid or thermal phosphoric acid usually, and its technology cost is higher, not by enterprise's mass production.And adopt phosphoric acid by wet process is raw material, and because of its impurity is high, technological operation is complicated, and with the agricultural level monoammonium phosphate fertilizer of ammonia react output, water-insoluble is used to spray drip irrigation system usually at 10-15%, can betting contest shower nozzle or pipeline.And produce the mother liquor difficult treatment, also be difficult to realize the large-scale industrialization continuous production.
In addition; In the existing water-soluble composite fertilizer that contains N, P, K nutritive element most of acidity a little less than; 1% aqueous solution pH is 7.0 like saltpetre; Potassium primary phosphate and monoammonium phosphate 1% pH value of water solution are 4.5, and these are slightly acidic or the very difficult alkaline soil that adapts to arid regions such as Xinjiang of China of the water-soluble fertilizer of neutral.
1% ureasulfuric acid pH value of water solution is 1, though be the water-soluble nitrogen sulphur of a kind of strongly-acid composite fertilizer, be applied to alkaline soil and will produce very significant effect, because of its strong water absorbability, is not easy to store transportation, has limited its application in fertilizer field.
In sum, press for a kind of low cost, ability continuous large-scale production and the convenient water-soluble fertilizer of strongly-acid that stores, transports at present, for the saline and alkaline regional crop of northwest droughts such as Xinjiang of China is supplied fertilizer source.
Summary of the invention
The object of the invention is to provide a kind of production low-cost, and the method for the special-purpose water-soluble fertilizer of the convenient alkaline soil that stores, transports, for the saline and alkaline regional crop of northwest droughts such as Xinjiang of China is supplied fertilizer source.
Technical scheme of the present invention: cross following mode and be achieved:
(1) preparation of ureasulfuric acid slurry:
In the 93-98wt% vitriolic, slowly add urea, the limit edged stirs, and controls slurry temperature 85-90 ℃ in the retort simultaneously, when slurry pH value is between 1.0-1.3, stops to add urea, obtains the ureasulfuric acid slurry;
(2) preparation of powder monoammonium phosphate;
(3) the ureasulfuric acid slurry is obtained work in-process with the powder monoammonium phosphate through liquid-solid the mixing; Wherein the ratio of ureasulfuric acid slurry and powder monoammonium phosphate is a monoammonium phosphate 50-95 weight part, ureasulfuric acid 5-50 weight part;
(4) work in-process promptly get the water-soluble fertilizer of the special-purpose strongly-acid of alkaline soil through dry, broken, screening.
As the preferred scheme of the present invention, the proportion 1.8-2.0kg/L of control ureasulfuric acid slurry in the such scheme, further preferred 1.85-1.93kg/L.
Among the present invention, monoammonium phosphate can adopt commercially available agricultural level product.
As the preferred scheme of the present invention; The said Powdered monoammonium phosphate of step in the such scheme (2) is got by following method preparation: slowly feed ammonia in the phosphoric acid by wet process; Open simultaneously and stir, when treating that the pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry, spraying drying promptly gets Powdered monoammonium phosphate.Said phosphoric acid by wet process is preferably handled through defluorinate.
Further preferably, control into tower AT 150-600 ℃ during spraying drying, go out 65-150 ℃ of tower AT.
Further preferably: during spraying drying, 350-500 ℃ of tower AT advanced in control, goes out 70-100 ℃ of tower AT.
As the preferred scheme of the present invention, step in the such scheme (3) is mixed through the ureasulfuric acid slurry evenly being sprayed to through spraying plant accomplish in the liquid-solid mixing tank that the powder monoammonium phosphate is housed.
As the preferred scheme of the present invention, the ratio of step in the such scheme (3) ureasulfuric acid slurry and powder monoammonium phosphate is: monoammonium phosphate 80-95 weight part, ureasulfuric acid 5-20 weight part.
In the present invention, the consumption of ureasulfuric acid is no more than 50wt%, if too much, the product water absorbability increases greatly, is inconvenient to store transportation; Certainly can not be low excessively, it is higher to be lower than 5% product water-insoluble and pH value, incompatibility dry spray fertigation system.
Through aforesaid method products obtained therefrom of the present invention is monoammonium phosphate (NH
4H
2PO
4), ureasulfuric acid (CO (NH
2)
2.H
2SO
4) mixture, its free-water is lower than 2%, preferably is lower than 1.5%.
In the inventive method, spray-dired temperature can influence the free water content of monoammonium phosphate, and temperature is crossed and low can be caused the monoammonium phosphate free-water after the spraying too much, is the muddy material, and it is rotten that the too high meeting of temperature causes monoammonium phosphate to decompose.
The product that adopts the inventive method to make is good fluidity pulverous water-soluble fertilizer product, monoammonium phosphate and a ureasulfuric acid mixture.The water absorbability of product is lower than 17%, and free-water is lower than 1.5wt%, and water-insoluble is lower than 1.5wt%, and pH is lower than 3.0.Preferably: water absorbability 10.2~12.8%, free-water 0.9~1.3wt%, water-insoluble 1.4~1.48wt%, pH 2.5~3.0.
Beneficial effect of the present invention:
(1) the present invention only need ureasulfuric acid slurry and Powdered fertilizer monoammonium phosphate uniform mixing is composite, dry, broken, sieve and promptly obtain acid water-soluble fertilizer product; And fertilizer monoammonium phosphate raw material adopts the phosphoric acid by wet process preparation; Therefore technical process of the present invention is simple, economical, easy to operate, can realize the large-scale industrialization continuous production.
(2) be the calcium phosphate precipitation that contains foreign ions such as Fe, Mg, Al, Ca in the fertilizer monoammonium phosphate of raw material production with phosphoric acid by wet process cheaply; These depositions make fertilizer monoammonium phosphate water-insoluble usually at 10-15%; Be used to spray drip irrigation system, can betting contest shower nozzle or pipeline.The present invention will make product after will having highly acid ureasulfuric acid and the composite spraying of fertilizer monoammonium phosphate, improve the acidity of fertilizer monoammonium phosphate, and product P H value is between 1.5~3.0; Simultaneously under this acidity value; Fe in the fertilizer monoammonium phosphate, Mg, Al, the isoionic calcium phosphate precipitation of Ca have become soluble salt; Not only increased the middle micronutrient element of fertilizer product, the water-insoluble that also makes product is between 0.5-1.5wt%, and therefore the water-soluble fertilizer of strongly-acid nitrogen phosphorus of the present invention can not only be improved alkaline soil; For the alkaline soil crop provides nutrient; Can also the well adapted dry or the drip irrigation spraying system of arid season, realize that liquid manure is integrated, reach water-saving, economize effect fertile, the saving of labor.
(3) ureasulfuric acid it be a kind of water-soluble fertilizer of strongly-acid nitrogen sulphur that can adapt to the spray drip irrigation system, but, be not easy to store transportation because of its strong water absorbability, be difficult to directly be used for fertilizer field.The present invention will have chemicalstability and less hygroscopic monoammonium phosphate mixes composite with ureasulfuric acid; Reduced the ureasulfuric acid rate of moisture absorption; Not only make the composite product water absorbability of the present invention that makes of mixing low; Convenient store transportation, also this has strong moisture absorption nitrogen sulphur composite fertilizer and well is applied to fertilizer field with ureasulfuric acid simultaneously.
Specific embodiment
The present invention is raw material with phosphoric acid by wet process cheaply with the ureasulfuric acid with strong moisture absorption, and it is low to produce a kind of pH, and water-insoluble is low, and product is difficult for the moisture absorption, has good flowability, the novel water-soluble compound manure that conveniently stores, transports and use.
The present invention is achieved through following mode:
(1) preparation of ureasulfuric acid slurry:
In the 93-98wt% vitriolic, slowly add urea, the limit edged stirs, and controls slurry temperature 85-90 ℃ in the retort simultaneously, when slurry pH value is between 1.0-1.3, stops to add urea, obtains the ureasulfuric acid slurry;
(2) preparation of powder monoammonium phosphate:
(3) ureasulfuric acid slurry and powder monoammonium phosphate are obtained work in-process through liquid-solid mixing tank; Wherein the ratio of ureasulfuric acid slurry and powder monoammonium phosphate is a monoammonium phosphate 50-95 weight part, ureasulfuric acid 5-50 weight part;
(4) work in-process promptly get the water-soluble fertilizer of the special-purpose strongly-acid of alkaline soil through dry, broken, screening.
As the preferred scheme of the present invention, the proportion 1.8-2.0kg/L of control ureasulfuric acid slurry in the such scheme, further preferred 1.85-1.93kg/L.
Among the present invention, monoammonium phosphate can adopt commercially available agricultural level product.
As the preferred scheme of the present invention; The said Powdered monoammonium phosphate of step in the such scheme (2) is got by following method preparation: slowly feed ammonia in the phosphoric acid by wet process; Open simultaneously and stir, when treating that the pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry, spraying drying promptly gets Powdered monoammonium phosphate.Said phosphoric acid by wet process is preferably handled through defluorinate.
Further preferably, control into tower AT 150-600 ℃ during spraying drying, go out 65-150 ℃ of tower AT.
Further preferably: during spraying drying, 350-500 ℃ of tower AT advanced in control, goes out 70-100 ℃ of tower AT.The free water content of spray-dired temperature effect the finished product, temperature are crossed and low can be caused the product free-water after the spraying too much, are the muddy material, and it is rotten that the too high meeting of temperature causes product to decompose.
As the preferred scheme of the present invention, step in the such scheme (3) is mixed through the ureasulfuric acid slurry evenly being sprayed to through spraying plant accomplish in the liquid-solid mixing tank that the powder monoammonium phosphate is housed.
As the preferred scheme of the present invention, the ratio of step in the such scheme (3) ureasulfuric acid slurry and powder monoammonium phosphate is: monoammonium phosphate 80-95 weight part, ureasulfuric acid 5-20 weight part.
In the present invention, the consumption of ureasulfuric acid is no more than 50wt%, if too much, the product water absorbability increases greatly, is inconvenient to store transportation; Certainly can not be low excessively, it is higher to be lower than 5% product water-insoluble and pH value, incompatibility dry spray fertigation system.
Through aforesaid method products obtained therefrom of the present invention is monoammonium phosphate (NH
4H
2PO
4), ureasulfuric acid (CO (NH
2)
2.H
2SO
4) mixture, its free-water is lower than 2%, preferably is lower than 1.5%.
In the inventive method, the free water content of spray-dired temperature effect monoammonium phosphate, temperature is crossed and low can be caused the monoammonium phosphate free-water after the spraying too much, is the muddy material, and it is rotten that the too high meeting of temperature causes monoammonium phosphate to decompose.
Hygroscopic testing method in following examples: detect by standard GB 4066.1-2004.
Water-insoluble is pressed the method test of the water-soluble fertile NY-1107-2010 of macroelement.
Free-water is pressed the method test of GB/T10209.3.
Embodiment 1
The concrete operations step is following:
(1) in having added 98% vitriolic, first reaction kettle, slowly adds urea; Open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted, and controls slurry temperature 85-90 ℃ in the retort; The control slurry pH value is between 1.0-1.3 the time; Stop to add urea, obtain the first raw material sulphuric acid urea slurry, and heat preservation for standby use;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia; Open simultaneously and stir, when treating that the pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry; Promptly obtain Powdered monoammonium phosphate raw material this slurry being carried out spraying drying, wherein 600 ℃ of tower ATs are advanced in control, go out 150 ℃ of tower ATs;
(3) with the raw material of (1) step and (2) step preparation by weight 40 parts of monoammonium phosphates: after the ratio that ureasulfuric acid is 60 parts is measured; Monoammonium phosphate is joined liquid-solid mixing tank; The ureasulfuric acid slurry joins in the atomization system, opens liquid-solid mixing tank wheelwork, starts spraying gun simultaneously; The ureasulfuric acid slurry evenly is sprayed in the monoammonium phosphate, obtains acid water-soluble fertile work in-process after uniform mixing is composite;
(4) work in-process promptly get product through dry, broken, screening.The products obtained therefrom index is seen table 1.
Embodiment 2
Concrete operations step of the present invention is following:
(1) in having added 98% vitriolic, first reaction kettle, slowly adds urea; Open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted, and controls slurry temperature 85-90 ℃ in the retort; The control slurry pH value is between 1.0-1.3; Stop to add urea, obtain the first raw material sulphuric acid urea slurry, and heat preservation for standby use;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia; Open simultaneously and stir, when treating that the pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry; Promptly obtain Powdered monoammonium phosphate raw material this slurry being carried out spraying drying, wherein 500 ℃ of tower ATs are advanced in control, go out 100 ℃ of tower ATs;
(3) with the raw material of (1) step and (2) step preparation by weight 50 parts of monoammonium phosphates: after the ratio that ureasulfuric acid is 50 parts is measured; Monoammonium phosphate is joined liquid-solid mixing tank; The ureasulfuric acid slurry joins in the atomization system, opens liquid-solid mixing tank wheelwork, starts spraying gun simultaneously; The ureasulfuric acid slurry evenly is sprayed in the monoammonium phosphate, obtains acid water-soluble fertile work in-process after uniform mixing is composite;
(4) work in-process promptly get product through dry, broken, screening.The products obtained therefrom index is seen table 1.
Embodiment 3
Concrete operations step of the present invention is following:
(1) in having added 93% vitriolic, first reaction kettle, slowly adds urea; Open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted, and controls slurry temperature 85-90 ℃ in the retort; The control slurry pH value is between 1.0-1.3; Stop to add urea, obtain the first raw material sulphuric acid urea slurry, and heat preservation for standby use;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia; Open simultaneously and stir, when treating that the pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry; Promptly obtain Powdered monoammonium phosphate raw material this slurry being carried out spraying drying, wherein 350 ℃ of tower ATs are advanced in control, go out 70 ℃ of tower ATs;
(3) with the raw material of (1) step and (2) step preparation by weight 75 parts of monoammonium phosphates: after the ratio that ureasulfuric acid is 25 parts is measured; Monoammonium phosphate is joined liquid-solid mixing tank; The ureasulfuric acid slurry joins in the atomization system, opens liquid-solid mixing tank wheelwork, starts spraying gun simultaneously; The ureasulfuric acid slurry evenly is sprayed in the monoammonium phosphate, obtains acid water-soluble fertile work in-process after uniform mixing is composite;
(4) work in-process promptly get product through dry, broken, screening.The products obtained therefrom index is seen table 1.
Embodiment 4
(1) in having added 98% vitriolic, first reaction kettle, slowly adds urea; Open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted, and controls slurry temperature 85-90 ℃ in the retort; Control slurry pH value is between 1.0-1.3; Stop to add urea, obtain the first raw material sulphuric acid urea slurry, and heat preservation for standby use;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia; Open simultaneously and stir, when treating that pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry; Promptly obtain Powdered monoammonium phosphate raw material this slurry being carried out spraying drying, wherein 150 ℃ of tower ATs are advanced in control, go out 65 ℃ of tower ATs;
(3) with the raw material of (1) step and (2) step preparation by weight 80 parts of monoammonium phosphates: after the ratio that ureasulfuric acid is 20 parts is measured; Monoammonium phosphate is joined liquid-solid mixing tank; The ureasulfuric acid slurry joins in the atomization system, opens liquid-solid mixing tank wheelwork, starts spraying gun simultaneously; The ureasulfuric acid slurry evenly is sprayed in the monoammonium phosphate, obtains acid water-soluble fertile work in-process after uniform mixing is composite;
(4) work in-process promptly get product through dry, broken, screening.The products obtained therefrom index is seen table 1.
Embodiment 5
(1) in having added 98% vitriolic, first reaction kettle, slowly adds urea; Open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted, and controls slurry temperature 85-90 ℃ in the retort; Control slurry pH value is between 1.0-1.3; Stop to add urea, obtain the first raw material sulphuric acid urea slurry, and heat preservation for standby use;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia; Open simultaneously and stir, when treating that pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry; Promptly obtain Powdered monoammonium phosphate raw material this slurry being carried out spraying drying, wherein 350 ℃ of tower ATs are advanced in control, go out 90 ℃ of tower ATs;
(3) with the raw material of (1) step and (2) step preparation by weight 95 parts of monoammonium phosphates: after the ratio that ureasulfuric acid is 5 parts is measured; Monoammonium phosphate is joined liquid-solid mixing tank; The ureasulfuric acid slurry joins in the atomization system, opens liquid-solid mixing tank wheelwork, starts spraying gun simultaneously; The ureasulfuric acid slurry evenly is sprayed in the monoammonium phosphate, obtains acid water-soluble fertile work in-process after uniform mixing is composite;
(4) work in-process promptly get product through dry, broken, screening.The products obtained therefrom index is seen table 1.
Embodiment 6
(1) in having added 98% vitriolic, first reaction kettle, slowly adds urea; Open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted, and controls slurry temperature 85-90 ℃ in the retort; Control slurry pH value is between 1.0-1.3; Stop to add urea, obtain the first raw material sulphuric acid urea slurry, and heat preservation for standby use;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia; Open simultaneously and stir, when treating that pH value is between 4.2-4.6, stop to feed ammonia; Obtain the monoammonium phosphate slurry; Promptly obtain Powdered monoammonium phosphate raw material this slurry being carried out spraying drying, wherein 450 ℃ of tower ATs are advanced in control, go out 120 ℃ of tower ATs;
(3) with the raw material of (1) step and (2) step preparation by weight 97 parts of monoammonium phosphates: after the ratio that ureasulfuric acid is 3 parts is measured; Monoammonium phosphate is joined liquid-solid mixing tank; The ureasulfuric acid slurry joins in the atomization system, opens liquid-solid mixing tank wheelwork, starts spraying gun simultaneously; The ureasulfuric acid slurry evenly is sprayed in the monoammonium phosphate, obtains acid water-soluble fertile work in-process after uniform mixing is composite;
(4) work in-process promptly get product through dry, broken, screening.The products obtained therefrom index is seen table 1.
Comparative Examples 1
This product is the Powdered fertilizer monoammonium phosphate product for preparing according to (2) one step process among the embodiment 1, and promptly product only contains fertilizer monoammonium phosphate raw material, does not contain ureasulfuric acid.The products obtained therefrom index is seen table 1.
Comparative Examples 2
This product is to prepare the ureasulfuric acid slurry product that oven dry obtains under 100 ℃ according to (1) one step process among the embodiment 1, and this product only contains ureasulfuric acid, does not contain fertilizer monoammonium phosphate raw material.The products obtained therefrom index is seen table 1.
Table 1
Project |
Monoammonium phosphate |
Ureasulfuric acid |
N |
P
2O
5 |
Water absorbability |
Free-water |
Water-insoluble |
pH |
Embodiment 1 |
40% |
60% |
12.73% |
24.5% |
21.2% |
1.60% |
0.38% |
1.2 |
Embodiment 2 |
50% |
50% |
11.30% |
30.5% |
16.3% |
1.48% |
0.47% |
1.5 |
Embodiment 3 |
75% |
25% |
10.50% |
46.3% |
13.1% |
1.21% |
1.32% |
2.0 |
Embodiment 4 |
80% |
20% |
10.30% |
49.4% |
12.8% |
1.33% |
1.4% |
2.5 |
Embodiment 5 |
95% |
5% |
10.23% |
58.6% |
10.2% |
0.98% |
1.48% |
3.0 |
Embodiment 6 |
97% |
3% |
10.20% |
57.1% |
9.1% |
0.73% |
5.7% |
4.4 |
Comparative Examples 1 |
100% |
0% |
9.55% |
58.0% |
8.89% |
0.78% |
6.1% |
4.6 |
Comparative Examples 2 |
0% |
100% |
16.0% |
- |
27.2% |
2.87% |
- |
1.0 |
Data can be found out from table 1, and the water-insoluble and the pH value of Comparative Examples 1 product all are higher than embodiment 1-6, and the interpolation of ureasulfuric acid is described, have reduced the water-insoluble and the pH value of monoammonium phosphate; The water absorbability of Comparative Examples 2 products is apparently higher than embodiment 1-6, and it is composite to explain that monoammonium phosphate mixes with ureasulfuric acid, can reduce the rate of moisture absorption of ureasulfuric acid single product.Table 1 also shows product water absorbability that embodiment 1 obtains obviously than being higher than embodiment 2-6, and this high-hygroscopicity product is difficult to store and transports; The insoluble China's dry alkaline soil that is difficult to water of the pH value of embodiment 6 products applies fertilizer; The proportioning that it can also be seen that specification product in the table is monoammonium phosphate 50-95wt%: ureasulfuric acid 5-50wt%, optimum ratio is: monoammonium phosphate 80-95wt%: ureasulfuric acid 5-20wt%.