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 the mother liquor difficult treatment in producing also is 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 low cost, and the special-purpose water-soluble fertilizer of the convenient alkaline soil that stores, transports, and supplies fertilizer source for the saline and alkaline regional crop of northwest droughts such as Xinjiang of China, can improve alkaline soil.
Technical scheme of the present invention: the present invention is raw material with phosphoric acid by wet process cheaply with the ureasulfuric acid with strong moisture absorption; 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:
Monoammonium phosphate (NH
4H
2PO
4), ureasulfuric acid (CO (NH
2)
2.H
2SO
4) and water mix and to be re-dubbed slurry, spraying drying then, cooling, screening promptly get product.Wherein the weight proportion of monoammonium phosphate and ureasulfuric acid is: monoammonium phosphate 50-95 part: ureasulfuric acid 5-50 part.Preferred scheme is: the weight proportion of monoammonium phosphate and ureasulfuric acid is: monoammonium phosphate 80-95 part: ureasulfuric acid 5-20 part.
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%.
Preferred scheme: water absorbability is lower than 17wt%, and water-insoluble is lower than 1.5wt%, and pH is lower than 3.0, can be used for the spray drip irrigation system of alkaline soil; Further preferred scheme, moist is 10.0~12.9wt%, free water content 0.9~1.3wt%, water-insoluble 1.35~1.5wt%, pH 2.5~3.0.
As the preferred scheme of the present invention, slowly logical ammonia is opened simultaneously and is stirred in phosphoric acid by wet process, and pH is between 4.2-4.6 in control, stops to feed ammonia, preparation and the monoammonium phosphate slip directly use, gained the finished product water insoluble matter content is lower.Said phosphoric acid by wet process is preferably handled through defluorinate.
As the preferred scheme of the present invention, adopt in the sulfuric acid of concentration 88-98% slowly to add urea, cooling and stirring simultaneously, pH is about 1 in control, preparation and the ureasulfuric acid slurry directly use.
Further, the present invention also provides the preparation method of the special-purpose water-soluble fertilizer of alkaline soil, it is characterized in that through following steps: add water by monoammonium phosphate, ureasulfuric acid and be mixed into spraying drying behind the slurry, cooling, screening obtain.The present invention can process slurry respectively with monoammonium phosphate, ureasulfuric acid and water, mixes the back spraying drying then, cooling, screening.Also can adopt other method to obtain monoammonium phosphate and ureasulfuric acid blended slurry.
As preferred scheme, the said slurry that is re-dubbed is to be obtained by following method:
(1) slowly logical ammonia in phosphoric acid by wet process is opened simultaneously and is stirred, and pH stops to feed ammonia when 4.2-4.6, preparation and the monoammonium phosphate slip;
(2) adopt the sulfuric acid of concentration 88-98wt%, add urea while stirring, control slurry temperature in the retort simultaneously, stop to add urea when pH reaches 0.9-1.1 less than 100 ℃, preparation and the ureasulfuric acid slurry;
(3) with (1) step with (2) step preparation and slurry according to weight ratio, monoammonium phosphate 50-95 part: the mixed of ureasulfuric acid 5-50 part and get, control slip proportion 1.2-1.5kg/L, preferably slip proportion 1.33-1.43kg/L.
In the inventive method, the free water content of spray-dired temperature effect the finished product, temperature is crossed and low can be caused the product free-water after the spraying too much, is the muddy material, and it is rotten that the too high meeting of temperature causes product to decompose.
As preferred scheme be: it is 150-350 ℃ that spray tower advances the tower AT, goes out 65-150 ℃ of tower freezing air temperature.Going out tower freezing air temperature can be through the inlet amount control of control spraying material.Further preferred scheme is: advance 180-250 ℃ of tower AT, go out 70-100 ℃ of tower AT.
Being used for spray-dired solid content of slurry can influence the slip flowability and spraying energy consumption in when spraying, those skilled in the art will know that and adopts what slurry solid content.The present invention can control the specific gravity control of slip at 1.2-1.5kg/L, between the preferred 1.33-1.43kg/L.
The product that adopts the inventive method to make is the pulverous water-soluble fertilizer product of good fluidity: monoammonium phosphate and ureasulfuric acid mixture.
Beneficial effect of the present invention:
(1) the present invention only needs that the fertilizer monoammonium phosphate is mixed slip after composite with ureasulfuric acid and sprays, cools off 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 the phosphoric acid by wet process, these depositions make fertilizer monoammonium phosphate water-insoluble usually at 10-15%, are 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 pH 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 itself is a kind of water-soluble fertilizer of strongly-acid nitrogen sulphur that can adapt to the spray drip irrigation system, but because of its strong water absorbability, is not easy to store transportation, is 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:
Monoammonium phosphate (NH
4H
2PO
4), ureasulfuric acid (CO (NH
2)
2.H
2SO
4) and water mix and to be re-dubbed slurry, spraying drying then, cooling, screening promptly get product.Wherein the weight proportion of monoammonium phosphate and ureasulfuric acid is: monoammonium phosphate 50-95 part: ureasulfuric acid 5-50 part.Preferred scheme is: the weight proportion of monoammonium phosphate and ureasulfuric acid is: monoammonium phosphate 80-95 part: ureasulfuric acid 5-20 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 the finished product, temperature is crossed and low can be caused the product free-water after the spraying too much, is the muddy material, and it is rotten that the too high meeting of temperature causes product to decompose.
As preferred scheme be: it is 150-350 ℃ that spray tower advances the tower AT, goes out 65-150 ℃ of tower freezing air temperature.Going out tower freezing air temperature can be through the inlet amount control of control spraying material.Further preferred scheme is: advance 180-250 ℃ of tower AT, go out 70-100 ℃ of tower AT.
Being used for spray-dired solid content of slurry can influence the slip flowability and spraying energy consumption in when spraying, those skilled in the art will know that and adopts what slurry solid content.The present invention can control the specific gravity control of slip at 1.2-1.5kg/L, between the preferred 1.33-1.43kg/L.
Among the present invention, monoammonium phosphate can adopt commercially available agricultural level product.
Certainly, the present invention is when specific embodiment, and slowly logical ammonia is opened simultaneously and stirred in phosphoric acid by wet process, and pH is between 4.2-4.6 in control, stops to feed ammonia, preparation and the monoammonium phosphate slip directly use, the products obtained therefrom water insoluble matter content is lower.Said phosphoric acid by wet process is preferably handled through defluorinate.
Among the present invention, ureasulfuric acid can adopt commercially available agricultural level product, also can adopt in the sulfuric acid of concentration 88-98% slowly to add urea, cooling and stirring simultaneously, pH is about 1 in control, preparation and slurry directly use.
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 add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control pH value stops to add urea about 1, obtain the first raw material sulphuric acid urea slip;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia, open simultaneously and stir, control pH value stops to feed ammonia between 4.2-4.6 the time, obtains the second raw material monoammonium phosphate slip;
(3) raw material that (1) step and (2) step is prepared is by weight 40 parts of monoammonium phosphates: the mixed that ureasulfuric acid is 60 parts is composite; Between the control slip proportion 1.33-1.43kg/L; Be input to the spray tower spraying drying then; Control tower turnover hot air temperature is: advance 180 ℃ of tower ATs, go out 70 ℃ of tower ATs; Obtain the water-soluble fertile work in-process of dry acidic;
(4) go out the tower material and promptly get product through boiling cooling, 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 88wt% vitriolic first reaction kettle, slowly add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control pH value stops to add urea when 1 left and right sides, obtain the first raw material sulphuric acid urea slip;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia, open simultaneously and stir, control pH value stops to feed ammonia between 4.2-4.6 the time, obtains the second raw material monoammonium phosphate slip;
(3) raw material that (1) step and (2) step is prepared is by weight 50 parts of monoammonium phosphates: the mixed that ureasulfuric acid is 50 parts is composite; Between the control slip proportion 1.33-1.43kg/L; Be input to the spray tower spraying drying then; Control tower turnover hot air temperature is: advance 150 ℃ of tower ATs, go out 65 ℃ of tower ATs; Obtain the water-soluble fertile work in-process of dry acidic;
(4) go out the tower material and promptly get product through boiling cooling, 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 98% vitriolic, first reaction kettle, slowly add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control pH value stops to add urea about 1, obtain the first raw material sulphuric acid urea slip;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia, open simultaneously and stir, control pH value stops to feed ammonia between 4.2-4.6 the time, obtains the second raw material monoammonium phosphate slip;
(3) raw material that (1) step and (2) step is prepared is by weight 75 parts of monoammonium phosphates: the mixed that ureasulfuric acid is 25 parts is composite; Between the control slip proportion 1.33-1.43kg/L; Be input to the spray tower spraying drying then; Control tower turnover hot air temperature is: advance 180 ℃ of tower ATs, go out 70 ℃ of tower ATs; Obtain the water-soluble fertile work in-process of dry acidic;
(4) go out the tower material and promptly get product through boiling cooling, screening.The products obtained therefrom index is seen table 1.
Embodiment 4
Concrete operations step of the present invention is following:
(1) in having added 90% vitriolic, first reaction kettle, slowly add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control pH value stops to add urea about 1, obtain the first raw material sulphuric acid urea slip;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia, open simultaneously and stir, control pH value stops to feed ammonia between 4.2-4.6 the time, obtains the second raw material monoammonium phosphate slip;
(3) raw material that (1) step and (2) step is prepared is by weight 80 parts of monoammonium phosphates: the mixed that ureasulfuric acid is 20 parts is composite; Between the control slip proportion 1.33-1.43kg/L; Be input to the spray tower spraying drying then; Control tower turnover hot air temperature is: advance 250 ℃ of tower ATs, go out 100 ℃ of tower ATs, obtain the water-soluble fertile work in-process of dry acidic;
(4) go out the tower material and promptly get product through boiling cooling, screening.The products obtained therefrom index is seen table 1.
Embodiment 5
Concrete operations step of the present invention is following:
(1) in having added 98% vitriolic, first reaction kettle, slowly add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control slip pH value stops to add urea about 1, obtain the first raw material sulphuric acid urea slip;
(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 second raw material monoammonium phosphate slip;
(3) raw material that (1) step and (2) step is prepared is by weight 95 parts of monoammonium phosphates: the mixed that ureasulfuric acid is 5 parts is composite; Between the control slip proportion 1.33-1.43kg/L; Be input to the spray tower spraying drying then; Control tower turnover hot air temperature is: advance 350 ℃ of tower ATs, go out 150 ℃ of tower ATs, obtain the water-soluble fertile work in-process of dry acidic;
(4) go out the tower material and promptly get product through boiling cooling, screening.The products obtained therefrom index is seen table 1.
Embodiment 6
Concrete operations step of the present invention is following:
(1) in having added 98% vitriolic, first reaction kettle, slowly add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control pH value stops to add urea about 1, obtain the first raw material sulphuric acid urea slip;
(2) in second reaction kettle that has added the defluorinate phosphoric acid by wet process, slowly feed ammonia, open simultaneously and stir, control pH value stops to feed ammonia between 4.2-4.6 the time, obtains the second raw material monoammonium phosphate slip;
(3) raw material that (1) step and (2) step is prepared is by weight 97 parts of monoammonium phosphates: the mixed that ureasulfuric acid is 3 parts is composite; Between the control slip proportion 1.33-1.43kg/L; Be input to the spray tower spraying drying then; Control tower turnover hot air temperature is: advance 180 ℃ of tower ATs, go out 70 ℃ of tower ATs; Obtain the water-soluble fertile work in-process of dry acidic;
(4) go out the tower material and promptly get product through boiling cooling, screening.The products obtained therefrom index is seen table 1.
Comparative Examples 1
The preparation method is basically with embodiment 1; Difference is not add in the reaction raw materials ureasulfuric acid; Promptly saved among the embodiment 1 and do not add ureasulfuric acid in (1) step and (3) step, the monoammonium phosphate slip with 100% is directly sprayed, cools off, is sieved and obtain product according to the spray condition of embodiment 1.The products obtained therefrom index is seen table 1.
Comparative Examples 2
In having added 98% vitriolic, first reaction kettle, slowly add urea, open and stir, the while limit adds the urea limit and removes the reaction heat that reaction is emitted; Slurry temperature in the control retort is less than 100 ℃; Control slip pH value stops to add urea about 1, obtain the ureasulfuric acid slurry; Directly spray, cool off, sieve and obtain product according to the spray condition of embodiment 1.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% |
12.70% |
24.0% |
22.3% |
1.62% |
0.4% |
1.2 |
Embodiment 2 |
50% |
50% |
11.50% |
30.0% |
16.4% |
1.5% |
0.5% |
1.5 |
Embodiment 3 |
75% |
25% |
10.90% |
46.0% |
13.1% |
1.2% |
1.3% |
2.1 |
Embodiment 4 |
80% |
20% |
10.36% |
49.0% |
12.9% |
1.3% |
1.35% |
2.5 |
Embodiment 5 |
95% |
5% |
10.20% |
58.0% |
10.0% |
0.9% |
1.5% |
3.0 |
Embodiment 6 |
97% |
3% |
10.27% |
57.4% |
9.2% |
0.75% |
5.8% |
4.3 |
Comparative Examples 1 |
100% |
0% |
9.58% |
58.4% |
9.0% |
0.8% |
6.0% |
4.5 |
Comparative Examples 2 |
0% |
100% |
16.2% |
- |
27.0% |
3.0% |
- |
1.1 |
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%.