CN102093113B - Production method of readily available and controlled release composite fertilizer containing three nitrogen elements - Google Patents
Production method of readily available and controlled release composite fertilizer containing three nitrogen elements Download PDFInfo
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- CN102093113B CN102093113B CN2011100211386A CN201110021138A CN102093113B CN 102093113 B CN102093113 B CN 102093113B CN 2011100211386 A CN2011100211386 A CN 2011100211386A CN 201110021138 A CN201110021138 A CN 201110021138A CN 102093113 B CN102093113 B CN 102093113B
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 112
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 51
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000013270 controlled release Methods 0.000 title abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 48
- 238000005469 granulation Methods 0.000 claims abstract description 46
- 230000003179 granulation Effects 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000007791 liquid phase Substances 0.000 claims abstract description 32
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000004202 carbamide Substances 0.000 claims abstract description 31
- 238000012216 screening Methods 0.000 claims abstract description 25
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 23
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 23
- 239000006012 monoammonium phosphate Substances 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011591 potassium Substances 0.000 claims abstract description 18
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 239000002686 phosphate fertilizer Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 48
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 34
- 229910021529 ammonia Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 238000010410 dusting Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000012856 packing Methods 0.000 claims description 10
- 239000013589 supplement Substances 0.000 claims description 9
- 238000013467 fragmentation Methods 0.000 claims description 8
- 238000006062 fragmentation reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000004176 ammonification Methods 0.000 claims description 7
- 235000015097 nutrients Nutrition 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 208000006558 Dental Calculus Diseases 0.000 claims description 4
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 4
- 238000002309 gasification Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006386 neutralization reaction Methods 0.000 abstract description 10
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000008187 granular material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- NFJCQBGAUBIGKV-UHFFFAOYSA-N nitro dihydrogen phosphate Chemical compound OP(O)(=O)O[N+]([O-])=O NFJCQBGAUBIGKV-UHFFFAOYSA-N 0.000 abstract 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- -1 amido nitrogen Chemical compound 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 238000001149 thermolysis Methods 0.000 abstract 1
- 230000008901 benefit Effects 0.000 description 11
- 210000003608 fece Anatomy 0.000 description 8
- 239000010871 livestock manure Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000006253 efflorescence Methods 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 238000005304 joining Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 206010037844 rash Diseases 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 241000208125 Nicotiana Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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Abstract
The invention discloses a production method of a readily available and controlled release composite fertilizer containing three nitrogen elements. The production method is as follows: raw materials containing nitric nitrogen, ammonium nitrogen and amido nitrogen are added in materials; in order to prevent that urea reacts with nitro phosphate fertilizer to generate too much urea nitrate and the production can not performed, ammonia gas is introduced in the granulation process according to different proportions to ammonify nitro phosphate fertilizer, reduce the generation of urea nitrate and increase the neutralization degree of monoammonium phosphate; and powdery fundamental fertilizers containing nitrogen, phosphorous and potassium are added to granulate, and then the composite fertilizer can be obtained through drying, cooling, screening and coating. In the production method of the invention, a lot of heat generated in the thermolysis of the nitro phosphate fertilizer and the neutralization heat of the reaction of ammonia gas and monoammonium phosphate are fully utilized to heat materials and increase the granulation temperature; and the viscosity of urea nitrate is utilized, the solubility of ammonium phosphate salt is increased, the quantity of the liquid phase for granulation can be satisfied, higher granulation rate can be realized without using other adhesive, the cost is reduced, the water content of the granulation material is significantly reduced, the drying energy consumption can be reduced and a large amount of energy consumption can be saved.
Description
Technical field
The present invention relates to a kind of production method of compound manure, be specifically related to a kind of production method that adds nitrophosphate fertilizer, urea and the granulation of industrial chemicals ammonia to make the quick-acting slow-release compound fertilizers that contain three kinds of nitrogens in the granulating method production technique, in the finished product, contain available nitrogen, nitric nitrogen, ammonia-state nitrogen and slow-release nitrogen, amidonitrogen.
Background technology
At present, along with the development of modern agriculture, the development of composite fertilizer is both at home and abroad occupied an leading position in chemical fertilizer industry, and in chemical fertilizer industry developed country, the composite fertilizer consumption has accounted for 70% ~ 80% of fertilizer amount.Composite fertilizer is mainly by the base fertilizer of nitrogenous, phosphorus, potassium; as urea, ammonium chloride, phosphorus ammonium, Repone K etc. after mixing; in tablets press; at certain temperature and amount of liquid phase; rely on the bounding force of self or add appropriate tackiness agent; the reunion granulating, then drying, cooling, screening are made compound fertilizer product.
Compound fertilizer production method mainly contains granulating method, spray granulating method, extrusion process and blending method etc., and they are all to belong to that base fertilizer carries out secondary processing and the content made has the composite fertilizer of the multiple elements such as nitrogen, phosphorus, potassium.
As shown in Figure 1; prior art utilizes the method for granulating method production Nitrogen, Phosphorus and Potassium to comprise the following steps: raw material such as Repone K, monoammonium phosphate, ammonium chloride, urea etc. are entered to rotary drum granulator after computer metering; simultaneously steam and water evenly are sprayed on the material in rotary drum granulator; after the physical mixed granulation; oven dry enters screening by cooling system; thoroughly after the crushing material of sieve, do not return to rotary drum granulator; screen sections enters packing machine thoroughly; carry out the anti-caking processing, after feed bin stores, pack.
Above-mentioned granulating method production technology is the widely used production method of China, the method production process is simple, operation is easy to grasp, but there is no chemical reaction between the production process Raw, be the physics granulation process, exist to make and expect that institute's water requirement is high, need to add a large amount of steaming G&Ws, increase follow-up drying load, and the granule strength of product is low.In product, contain a kind of nitrogen (ammonium nitrogen) or two kinds of nitrogens (ammonium nitrogen and amidonitrogen), the main source of ammonium nitrogen is ammonium chloride, the source of amidonitrogen is urea, potassium usually source is mostly Repone K, in product, chloride ion content is high, is two chlorine productss, and the field crop long-term application can cause soil compaction, crop failure, and be not suitable for the cash crop such as vegetables, fruit tree, tobacco.
Summary of the invention
the purpose of this invention is to provide the production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens based on the production of granulating method, in production, do not add ammonium chloride, add nitrophosphate fertilizer and urea, in product, contain nitric nitrogen, ammonium nitrogen, three kinds of nitrogens of amidonitrogen, the nitrogen that namely has immediate effect in three kinds of nitrogens also has slow-release nitrogen, urea adds in the solid mode, and as the required master batch of granulating, by other material, wrapped up layer by layer, by the chemical reaction that utilizes storeroom, increase granule strength, make the housing of coated urea more solid, control the release rate of amidonitrogen, make product have better slow release effect.
Another object of the present invention is by adding nitrophosphate fertilizer, to obtain nitric nitrogen, and take full advantage of itself and urea reaction and generate the viscosity of urea nitrate as the granulating liquid phase, utilize the poor heat stability of nitrophosphate fertilizer, heat is decomposed a large amount of heat of generation and is added thermal material and improve prilling temperature, takes full advantage of its chemical reaction heat and reduces product moisture, reduces drying load, can realize without drying process, the compound manure of finally making has higher intensity.
Another object of the present invention is by adding ammonia, in granulation process, completes the ammonification of nitrophosphate fertilizer, prevents too much urea nitrate, makes to produce normally to carry out.
Further purpose of the present invention is that the tail gas to production process carries out carrying out washing treatment, and, to the washing water recycling, is used for supplementing the amount of liquid phase of granulating institute palpus.So that waste gas, wastewater zero discharge in composite fertilizer's production process make more friendly environment of composite fertilizer's production process.
In order to solve the problems of the technologies described above; the technical solution used in the present invention is a kind of production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens; in granulating method composite fertilizer produces; add nitrophosphate fertilizer to obtain nitric nitrogen; gas ammonia is directly led in the bed of material of rotary drum granulator; complete the ammonium processing of nitrophosphate fertilizer; control the quality that reaction generates urea nitrate; the powdery base fertilizer granulation of, phosphorus nitrogenous with urea and other, potassium, granulation obtains containing nitrogen, phosphorus, the K compound fertilizer of three kinds of nitrogens by dry, cooling, screening, coating.
Specifically, the described production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens comprises the following steps:
(1) in granulating method composite fertilizer produces, the powdery base fertilizer of nitrophosphate fertilizer and urea and other is nitrogenous, phosphorus, potassium enters rotary drum granulator after computer metering, after liquid ammonia gasification by mass percent 3%-4% sum of the mass percent 8-13% that accounts for the nitrophosphate fertilizer input amount and other phosphate fertilizer input amounts, lead in the bed of material of rotary drum granulator, in rotary drum granulator, complete ammonification and the material granulation process of nitrophosphate fertilizer, in rotary drum granulator, temperature of charge is controlled at 80-90 ℃, granulation time 3～7min;
(2) after granulation, material enters dryer, and the dryer temperature is controlled at 90-100 ℃, drying time 20～40 min;
(3) after the oven dry, it is cooling that material enters cooling system, cooling rear respectively through dusting cover screening and scalping screening; pulverulent material after dusting cover returns to tablets press with the macrobead after scalping together with fragmentation; salable product enter packing machine, carry out the anti-caking processing, after feed bin stores, pack.
In production process, add nitrophosphate fertilizer and urea, utilize the viscosity of urea nitrate as the required liquid phase of granulating, utilize the nitrophosphate fertilizer poor heat stability, heat is decomposed the amount of heat that produces and is added thermal material, and supplements the required amount of liquid phase of granulating with granulation tail vapour washing water.
Between the sieve diameter 2.0-3.0mm of dusting cover screening, between the sieve diameter 4.0-4.5mm of scalping screening.
The described powdery base fertilizer that contains other nitrogen, phosphorus, potassium is several mixtures in monoammonium phosphate, general calcium, ammonium sulfate, Repone K, vitriolate of tartar, the base fertilizer kind that adds and add-on need be looked the nutrient, moisture of the finished product and determined, the product of production is the monochloro product.
In the finished product, contain nitric nitrogen, ammonia-state nitrogen and amidonitrogen, and do not add ammonium chloride.
The production method that the present invention contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens compared with prior art has the following advantages:
1, in the product of producing, contain three kinds of nitrogens: nitric nitrogen, ammonium nitrogen and amidonitrogen, wherein nitric nitrogen, ammonium nitrogen are that available nitrogen, amidonitrogen are slow-release nitrogen.Urea adds in the solid mode, and, as the required master batch of granulating, by other material, is wrapped up layer by layer, by the chemical reaction that utilizes storeroom, increase granule strength, make the housing of coated urea more solid, control the release rate of amidonitrogen, make product have better slow release effect.The crop scope of application is wider, and not only applicable field crop, can also be applicable to the economic class crops such as vegetables, fruit tree, tobacco.After incorporation of fertilizerin the soil, nitric nitrogen started to discharge in 5-7 days, and ammonium nitrogen started to discharge in 10-15 days, and amidonitrogen starts after 15 days to discharge, and had guaranteed that crop is omnidistance for nutrient.
2, the viscosity of utilizing urea nitrate, as the required liquid phase of granulating, is utilized the nitrophosphate fertilizer poor heat stability, and heat is decomposed the amount of heat that produces and added thermal material.
3, utilize gas ammonia in rotary drum granulator, to complete the ammonification of nitrophosphate fertilizer; and utilize the neutralization heat of excessive gas ammonia and monoammonium phosphate reaction to add thermal material, improve simultaneously the solubleness of ammonium phosphate salt, to increase the required amount of liquid phase of granulating; the granulation material moisture obviously reduces, and reduces drying load.
4, compound fertilizer product of the present invention: contain the monochloro product of three kinds of nitrogens, the smooth rounding of particle, intensity is high, prevented from caking, anti-storage.
5, in production process by tail gas is carried out to carrying out washing treatment, and utilize washing water to supplement the required amount of liquid phase of granulating.Accomplished waste gas, wastewater zero discharge in composite fertilizer's production process, made more friendly environment of composite fertilizer's production process.
While 6, producing, without adding again any tackiness agent just can reach good balling-up situation, realize without the stopping composition granulation, reduce production costs.
The accompanying drawing explanation
Fig. 1 is the method flow diagram that prior art is utilized granulating method production Nitrogen, Phosphorus and Potassium.
Fig. 2 is the production method schema that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail:
As shown in Figure 1, the present invention contains the production method of the quick-acting slow-release compound fertilizers of three kinds of nitrogens, in material, add the raw material that contains nitric nitrogen, ammonium nitrogen, amidonitrogen, the source of nitric nitrogen is that the source of nitrophosphate fertilizer, ammonium nitrogen is monoammonium phosphate, ammonium sulfate, nitrophosphate fertilizer etc., the source of amidonitrogen is urea, and wherein nitrophosphate fertilizer contains nitric nitrogen and two kinds of nitrogens of ammonium nitrogen.And the viscosity of utilizing urea nitrate is as the granulating liquid phase, for preventing from reacting the too much urea nitrate of generation, make to produce and can't carry out, need in granulation process, pass into gas ammonia according to different proportionings, nitrophosphate fertilizer is carried out to ammonification, to control urea nitrate, generate quality, and increase the degree of neutralization of monoammonium phosphate, then the powdery base fertilizer granulation of, phosphorus nitrogenous with other, potassium, granulation obtains containing nitrogen, phosphorus, the K compound fertilizer of three kinds of nitrogens by dry, cooling, screening, coating.
Specifically, the described production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens comprises the following steps:
(1) in the quick-acting slow-release compound fertilizers of three kinds of nitrogens of granulating method are produced; add nitrophosphate fertilizer to obtain nitric nitrogen; by the mass percent 8-13% that accounts for the nitrophosphate fertilizer input amount, will after liquid ammonia gasification, lead to ammonification nitrophosphate fertilizer in the bed of material of rotary drum granulator, by the mass percent 3%-4% that accounts for the monoammonium phosphate input amount, will after liquid ammonia gasification, lead to the solubleness that increases monoammonium phosphate in the bed of material of rotary drum granulator.And substitute the supplementary required amount of liquid phase of granulating of steam with the granulation washing water, in production process, do not need to add tackiness agent.
(2) urea and other is nitrogenous, the powdery base fertilizer of phosphorus, potassium enters rotary drum granulator after computer metering; with gas ammonia, in rotary drum granulator, complete the ammoniation-granulation process; in granulation process, take full advantage of the viscosity of utilizing urea nitrate and the solubleness that improves ammonium phosphate salt as the required liquid phase of granulating; utilize the nitrophosphate fertilizer poor heat stability; heat is decomposed the amount of heat of generation and the neutralization heat of gas ammonia and monoammonium phosphate reaction adds thermal material, and supplements the required amount of liquid phase of granulating with granulation tail vapour washing water.In rotary drum granulator, temperature of charge is controlled at 80-90 ℃, granulation time 3～7min;
(3) after granulation, material enters dryer, and the dryer temperature is controlled at 90-100 ℃, drying time 20～40 min;
(4) after the oven dry, it is cooling that material enters cooling system, cooling rear respectively through dusting cover screening and scalping screening; pulverulent material after dusting cover returns to tablets press with the macrobead after scalping together with fragmentation; salable product enter packing machine, carry out the anti-caking processing, after feed bin stores, pack.
Between the sieve diameter 2.0-3.0mm of dusting cover screening, between the sieve diameter 4.0-4.5mm of scalping screening.
Described other are nitrogenous, several mixtures in phosphorus, the powdery base fertilizer monoammonium phosphate of potassium, general calcium, ammonium sulfate, Repone K, vitriolate of tartar, the base fertilizer kind that adds and add-on need be looked nutrient, the moisture of the finished product and be determined, the product of producing is the monochloro product, do not add ammonium chloride, in the finished product, contain nitric nitrogen, ammonia-state nitrogen and amidonitrogen.Urea adds in the solid mode, and, as the required master batch of granulating, by other material, is wrapped up layer by layer, by the chemical reaction that utilizes storeroom, increase granule strength, make the housing of coated urea more solid, control the release rate of amidonitrogen, make product have better slow release effect.
Described nitrophosphate fertilizer is if particulate state needs to add after fragmentation.
principle of the present invention is: in production process, add nitrophosphate fertilizer and urea, and in granulation process, pass into gas ammonia, to control the too much urea nitrate of generation, production process can't be carried out, the solubleness that takes full advantage of the viscosity of urea nitrate and improve ammonium phosphate salt is as the required liquid phase of granulating, utilize the nitrophosphate fertilizer poor heat stability, heat is decomposed the amount of heat of generation and the neutralization heat of gas ammonia and monoammonium phosphate reaction adds thermal material, and supplement the required amount of liquid phase of granulating with granulation tail vapour washing water, nitrogenous with other, phosphorus, the potassium powdered fertilizer, at higher temperature, the granulating of reuniting under the effect of rotary drum granulator, containing ammonium chloride not in raw material, producing product is the monochloro product, can adapt to for cash crop.
CO (NH
2)
2+ HNO
3=CO (NH
2)
2HNO
3(urea nitrate)
NH3+(NH
4) H
2PO
4=(NH
4) 2HPO
4+ heat
During composite fertilizer produces, the product of different ingredients, the required amount of liquid phase of its granulating is different, and the solubleness of various raw materials is to increase along with the rising of temperature, utilize gas ammonia and monoammonium phosphate and nitrophosphate fertilizer heat to decompose the solubleness that the amount of heat that produces improves other raw material, this has also increased the required amount of liquid phase of granulating.But also can adjust the ammonia consumption according to different formula (nitrophosphate fertilizer used what), control urea nitrate and reaction heat.Like this, on technique, can adopt cryodrying, even without drying process, thereby significantly reduce drying load.Utilize simultaneously the increase of the solubleness of the viscosity of urea nitrate and monoammonium phosphate, without adding again any tackiness agent just can reach good balling-up situation.
The present invention contains the production method of the quick-acting slow-release compound fertilizers of three kinds of nitrogens, and described raw material is nitrophosphate fertilizer, urea, ammonium sulfate, monoammonium phosphate, general calcium, Repone K, vitriolate of tartar etc.The base fertilizer kind that adds and add-on need be looked the nutrient, moisture of the finished product and determined, if nitrophosphate fertilizer is particulate state, need to add after fragmentation.
The present invention contains the production method of the quick-acting slow-release compound fertilizers of three kinds of nitrogens, and the state that described base fertilizer enters tablets press is solid, has so just reduced the production processes such as urea melting.
Due to the Fertilizer application variation in season, the compound manure waiting time is longer, therefore can produce efflorescence.The reason of a material efflorescence is exactly that product strength is low by analysis, moisture is high, and the product that the production method that adopts the present invention to contain the quick-acting slow-release compound fertilizers of three kinds of nitrogens is produced, more than product particle intensity can reach 20N, therefore, there is not the problem of particle efflorescence in moisture≤1.8%.
The present invention contains the production method of the quick-acting slow-release compound fertilizers of three kinds of nitrogens, owing to taking full advantage of when nitrophosphate fertilizer decomposes amount of heat and the ammonia react heat that produces, the dryer temperature is controlled at 90-100 ℃ just can guarantee normal production, even add more urea, can not produce a large amount of liquid phases of bringing due to the material melting yet, can not affect follow-up drying process.And traditional granulating method production technique is owing to adding a large amount of steaming G&Ws, and the dryer temperature need to be controlled at 150-200 ℃, like this can be because the urea melting produces a large amount of liquid phases, and when serious, impact is produced and is normally carried out.
In addition, because the compound manure water absorbability is stronger, while depositing, easily lump.In order to prevent caking, need to carry out the anti-caking processing to the fertilizer after screening.Can apply powder, coating processes.
The invention will be further elaborated below by example:
Embodiment 1:18-18-18 product
gas ammonia (contains N 82.3%, mass percent, 30 kilograms down together), after metering with joining in the rotary drum granulator bed of material, simultaneously through computer metering, add urea (containing N46.2) 120 kg, powdery monoammonium phosphate (contains N 11%, P2O5 46%) 335 kilograms, nitrophosphate fertilizer (contains N 26%, P2O5 12.6%) 220 kilograms, 315 kilograms, Repone K (containing K2O56%), above-mentioned pulverulent material mixes in tablets press with gas ammonia, the solubleness that takes full advantage of the viscosity of urea nitrate in granulation process and improve ammonium phosphate salt is as the required liquid phase of granulating, utilize the nitrophosphate fertilizer poor heat stability, heat is decomposed the amount of heat of generation and the neutralization heat of gas ammonia and monoammonium phosphate reaction adds thermal material, and supplement the required amount of liquid phase of granulating with granulation tail vapour washing water, in rotary drum granulator, temperature of charge is controlled at 85 ℃, after the 3min granulation, enter drying machine, drying machine inlet gas temperature is 100 ℃, dry 25 minutes, after drying, carry out cooling, cooling rear respectively through the screening of sieve diameter 2.0-3.0mm dusting cover and sieve diameter 4.0-4.5mm scalping screening, pulverulent material after dusting cover returns to tablets press with the macrobead after scalping together with fragmentation, salable product enter packing machine, carry out the anti-caking processing, coating, packing, obtain the compound manure that granularity is 2-4.5mm.Product is moisture 1.6%, and intensity 21N contains N-P2O5---and K2O is 17.4-18.2-18.0, and particle is smooth, rounding.
Embodiment 2:18-20-10 high-phosphorus products
gas ammonia (contains N 82.3%, mass percent, 40 kilograms down together), after metering with joining in the rotary drum granulator bed of material, simultaneously through computer metering, add 85 kilograms, urea (containing N46.2), powdery monoammonium phosphate (contains N 11%, P2O5 46%) 300 kilograms, nitrophosphate fertilizer (contains N 26%, P2O5 12.6%) 300 kilograms, general calcium 120 kg (containing P2O5 17%), 175 kilograms, Repone K (containing K2O57%), above-mentioned pulverulent material mixes in tablets press with gas ammonia, the solubleness that takes full advantage of the viscosity of urea nitrate in granulation process and improve ammonium phosphate salt is as the required liquid phase of granulating, utilize the nitrophosphate fertilizer poor heat stability, heat is decomposed the amount of heat of generation and the neutralization heat of gas ammonia and monoammonium phosphate reaction adds thermal material, and supplement the required amount of liquid phase of granulating with granulation tail vapour washing water, in rotary drum granulator, temperature of charge is controlled at 90 ℃, after the 3min granulation, enter drying machine, drying machine inlet gas temperature is 100 ℃, dry 30 minutes, after drying, carry out cooling, cooling rear respectively through the screening of sieve diameter 2.0-3.0mm dusting cover and sieve diameter 4.0-4.5mm scalping screening, pulverulent material after dusting cover returns to tablets press with the macrobead after scalping together with fragmentation, salable product enter packing machine, carry out the anti-caking processing, coating, packing, obtain the compound manure that granularity is 2-4.5mm.Product is moisture 1.7%, and intensity 23N contains N-P2O5---and K2O is 18.3-19.6-10.0, and particle is smooth, rounding, pure white.
The high nitrogen product of embodiment 3:28-12-10
gas ammonia (contains N 82.3%, mass percent, 48 kilograms down together), after metering with joining in the rotary drum granulator bed of material, simultaneously through computer metering, add 295 kilograms, urea (containing N46.2), powdery monoammonium phosphate (contains N 11%, P2O5 46%) 190 kilograms, 305 kilograms of nitrophosphate fertilizers (contain N 26%, P2O5 12.6%), 170 kilograms, Repone K (containing K2O57%), above-mentioned pulverulent material mixes in tablets press with gas ammonia, the solubleness that takes full advantage of the viscosity of urea nitrate in granulation process and improve ammonium phosphate salt is as the required liquid phase of granulating, utilize the nitrophosphate fertilizer poor heat stability, heat is decomposed the amount of heat of generation and the neutralization heat of gas ammonia and monoammonium phosphate reaction adds thermal material, and supplement the required amount of liquid phase of granulating with granulation tail vapour washing water, in rotary drum granulator, temperature of charge is controlled at 80 ℃, after the 3min granulation, enter drying machine, drying machine inlet gas temperature is 90 ℃, dry 20 minutes, after drying, carry out cooling, cooling rear respectively through the screening of sieve diameter 2.0-3.0mm dusting cover and sieve diameter 4.0-4.5mm scalping screening, pulverulent material after dusting cover returns to tablets press with the macrobead after scalping together with fragmentation, salable product enter packing machine, carry out the anti-caking processing, coating, packing, obtain the compound manure that granularity is 2-4.5mm.Product is moisture 1.5%, and intensity 22N contains N-P2O5---and K2O is 27.6-12.4-9.7, and particle is smooth, rounding.
Three kinds of nitrogen granulation of compound fertilizer are to introduce industrial chemicals liquefied ammonia, the solubleness that takes full advantage of the viscosity of urea nitrate and improve ammonium phosphate salt is as the required liquid phase of granulating, and utilize reaction heat to improve the solubleness of other raw material, this has also increased the required amount of liquid phase of granulating, but also can adjust the ammonia consumption according to different formula (nitrophosphate fertilizer used what), increase amount of liquid phase and reaction heat, with other, containing three kinds of nitrogen compound manure of fertilizer processing and fabricating of the elements such as nitrogen, phosphorus, potassium, is chemical reaction granulating technology.The granulation balling ratio of ammonification technique can reach 60-80%, and common process only has 40-60%.
The invention solves the product nitrogen that traditional granulating method makes single, can not be omnidistance in crop growth period chlorion is high for nutrient, cash crop can not be used, the field crop long-term application causes soil compaction, the problems such as crop failure.And overcome the shortcoming that the traditional product energy consumption is high, outward appearance is coarse, balling ratio is low, product cost is high, reduced costs to greatest extent, improved to greatest extent product quality.By adding aborning industrial chemicals ammonia, nitrophosphate fertilizer and urea, the solubleness that takes full advantage of the viscosity of urea nitrate and improve ammonium phosphate salt is as the required liquid phase of granulating, utilize the nitrophosphate fertilizer poor heat stability, heat is decomposed the amount of heat of generation and the neutralization heat of gas ammonia and monoammonium phosphate reaction adds thermal material, and supplement the required amount of liquid phase of granulating with granulation tail vapour washing water, change traditional way and need to add the way of a large amount of steaming G&Ws as the granulating amount of liquid phase, and need not add tackiness agent, product cost has reduction significantly.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (6)
1. production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens, it is characterized in that, in granulating method composite fertilizer produces, nitrophosphate fertilizer and urea and other is nitrogenous, phosphorus, potassium but the powdery base fertilizer that do not contain ammonium chloride is sent into rotary drum granulator, and gas ammonia is directly led in the bed of material of rotary drum granulator to the urea nitrate of controlling urea and nitrophosphate fertilizer reaction generation, nitrogenous with other, phosphorus, potassium but do not contain the powdery base fertilizer granulation of ammonium chloride, granulation is by drying, cooling, screening, coating obtains containing the nitrogen of three kinds of nitrogens, phosphorus, K compound fertilizer.
2. the production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens according to claim 1, is characterized in that, comprises the following steps:
(1) in granulating method composite fertilizer produces, nitrophosphate fertilizer and urea and other is nitrogenous, phosphorus, potassium but the powdery base fertilizer that do not contain ammonium chloride enters rotary drum granulator after computer metering, after liquid ammonia gasification by mass percent 3%-4% sum of the mass percent 8-13% that accounts for the nitrophosphate fertilizer input amount and other phosphate fertilizer input amounts, lead in the bed of material of rotary drum granulator, in rotary drum granulator, complete ammonification and the material granulation process of nitrophosphate fertilizer, in rotary drum granulator, temperature of charge is controlled at 80-90 ℃, granulation time 3～7min;
(2) after granulation, material enters dryer, and the dryer temperature is controlled at 90-100 ℃, drying time 20～40 min;
(3) after the oven dry, it is cooling that material enters cooling system, cooling rear respectively through dusting cover screening and scalping screening; pulverulent material after dusting cover returns to tablets press with the macrobead after scalping together with fragmentation; salable product enter packing machine, carry out the anti-caking processing, after feed bin stores, pack.
3. the production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens according to claim 2, is characterized in that, between the sieve diameter 2.0-3.0mm of dusting cover screening, between the sieve diameter 4.0-4.5mm of scalping screening.
4. the production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens according to claim 2, it is characterized in that, described other is nitrogenous, phosphorus, potassium but the powdery base fertilizer that do not contain ammonium chloride is several mixtures in monoammonium phosphate, general calcium, ammonium sulfate, Repone K, vitriolate of tartar, the base fertilizer kind that adds and add-on need be looked the nutrient, moisture of the finished product and determined, the product of production is the monochloro product.
5. the production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens according to claim 1 and 2, is characterized in that, described urea adds in the solid mode, and as the required master batch of granulating.
6. the production method that contains the quick-acting slow-release compound fertilizers of three kinds of nitrogens according to claim 2, is characterized in that, in step (1), with granulation tail vapour washing water, supplements the required amount of liquid phase of granulating.
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| CN102515911A (en) * | 2011-11-21 | 2012-06-27 | 安徽欧杰利生态肥业有限公司 | High-nitrogen composite fertilizer and preparation method thereof |
| CN102491858A (en) * | 2011-12-20 | 2012-06-13 | 上海化工研究院 | Method for manufacturing urea-based nitrate slow-releasing compound fertilizer |
| CN103193535A (en) * | 2013-04-18 | 2013-07-10 | 天津芦阳化肥股份有限公司 | Quick-acting slow-released compound fertilizer and preparation method thereof |
| CN103193548B (en) * | 2013-05-03 | 2014-11-12 | 辽宁施壮肥业有限公司 | Organic-inorganic multi-element pollution-free compound fertilizer and preparation method thereof |
| CN103265381A (en) * | 2013-06-19 | 2013-08-28 | 天津芦阳化肥股份有限公司 | Green environment-friendly compound fertilizer prepared from three kinds of organic-inorganic nitrogen and preparation method thereof |
| CN103483110B (en) * | 2013-09-06 | 2015-09-09 | 天津芦阳化肥股份有限公司 | Whole process is for nutrient compound manure and preparation method thereof |
| CN103664370A (en) * | 2013-12-05 | 2014-03-26 | 中盐安徽红四方股份有限公司 | Urea-ammonium mixed nitrogen fertilizer and production method thereof |
| CN104072246B (en) * | 2014-07-11 | 2016-06-08 | 四川蓥峰实业有限公司 | The spray granulating production technique of a kind of composite fertilizer containing nitric nitrogen |
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| CN105948994A (en) * | 2016-05-16 | 2016-09-21 | 安徽省龙晨肥业有限公司 | Urea-based compound fertilizer containing high-activity minerals |
| CN107935703A (en) * | 2017-12-04 | 2018-04-20 | 中化化肥有限公司成都研发中心 | Urinate base nitro binary compound fertilizer containing nitrogen and potassium production method |
| CN111303896B (en) * | 2020-02-04 | 2021-09-03 | 中化农业（临沂）研发中心有限公司 | Saline-alkali soil conditioner and method for preparing saline-alkali soil conditioner by utilizing phosphate rock tailings and low-rank coal |
| CN111574293A (en) * | 2020-04-20 | 2020-08-25 | 杨新正 | Special fertilizer containing all-nitrogen for rice and preparation method thereof |
| CN114671722A (en) * | 2022-04-25 | 2022-06-28 | 杨云芳 | Preparation process of degradable strong water-absorption double-slow-release water-retention fertilizer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0039241A2 (en) * | 1980-04-28 | 1981-11-04 | Omnia Fertilizer Limited | Method and apparatus for producing nitrophosphate fertilizers |
| CN1417174A (en) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | Direct urea solution spraying and pelletizing process of producing composite fertilizer |
| CN1785936A (en) * | 2005-12-13 | 2006-06-14 | 天津芦阳化肥股份有限公司 | Shell body nitrogen fixing slow release composite fertilizer |
| CN101717289A (en) * | 2009-11-30 | 2010-06-02 | 天津芦阳化肥股份有限公司 | Method for producing Nitrogen-Phosphorus-Potassium compound fertilizer by ammonia and acid tubular reactor |
-
2011
- 2011-01-19 CN CN2011100211386A patent/CN102093113B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0039241A2 (en) * | 1980-04-28 | 1981-11-04 | Omnia Fertilizer Limited | Method and apparatus for producing nitrophosphate fertilizers |
| CN1417174A (en) * | 2002-12-11 | 2003-05-14 | 南化集团研究院 | Direct urea solution spraying and pelletizing process of producing composite fertilizer |
| CN1785936A (en) * | 2005-12-13 | 2006-06-14 | 天津芦阳化肥股份有限公司 | Shell body nitrogen fixing slow release composite fertilizer |
| CN101717289A (en) * | 2009-11-30 | 2010-06-02 | 天津芦阳化肥股份有限公司 | Method for producing Nitrogen-Phosphorus-Potassium compound fertilizer by ammonia and acid tubular reactor |
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