WO2017151017A1 - Engrais npk contenant du phosphore, du potassium et de l'azote et procédé de préparation d'un engrais npk contenant du phosphore, du potassium et de l'azote granulé - Google Patents

Engrais npk contenant du phosphore, du potassium et de l'azote et procédé de préparation d'un engrais npk contenant du phosphore, du potassium et de l'azote granulé Download PDF

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WO2017151017A1
WO2017151017A1 PCT/RU2017/000108 RU2017000108W WO2017151017A1 WO 2017151017 A1 WO2017151017 A1 WO 2017151017A1 RU 2017000108 W RU2017000108 W RU 2017000108W WO 2017151017 A1 WO2017151017 A1 WO 2017151017A1
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Prior art keywords
potassium
fertilizer
decomposition
npk
phosphate salt
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PCT/RU2017/000108
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English (en)
Inventor
Alexander Vladimirovich TUGOLUKOV
Dmitry Vladimirovich VALYSHEV
Oleg Lvovich ELIN
Peter Lehocky
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Mineral And Chemical Company Eurochem, Joint Stock Company
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Priority to CN201780005551.9A priority Critical patent/CN108473380A/zh
Publication of WO2017151017A1 publication Critical patent/WO2017151017A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
    • C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
    • C05B11/08—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using sulfuric acid
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C1/00—Ammonium nitrate fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05B—PHOSPHATIC FERTILISERS
    • C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
    • C05B1/04—Double-superphosphate; Triple-superphosphate; Other fertilisers based essentially on monocalcium phosphate
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05

Definitions

  • NPK-fertilizer ( "azophoska” , “nitroammophoska” ) is a complex fertilizer possessing high economic efficiency and intended for use in growing different crops and in almost any soil.
  • NPK type is characterized by mass fractions of nitrogen, phosphorus and potassium in a fertilizer.
  • the present invention relates to production of granulated NPK-fertilizers from phosphate salt containing up to 99% fluorapatite, in particular said phosphate salt is a mixture of CaHP0 4 x nH 2 0 (dicalcium phosphate) and Ca 5 (P0 4 ) 3 F ( fluorapatite) , where n is 0 to 2, fluorapatite Ca 5 (POi) 3 F content in phosphate salt is 27% to 99%, wherein the process allows to use various potassium and ammonium salts as sources of nutrients in the fertilizer .
  • phosphate salt is a mixture of CaHP0 4 x nH 2 0 (dicalcium phosphate) and Ca 5 (P0 4 ) 3 F ( fluorapatite) , where n is 0 to 2, fluorapatite Ca 5 (POi) 3 F content in phosphate salt is 27% to 99%, wherein the process allows to use various potassium and ammonium salt
  • the invention also relates to a continuous process for producing a granulated NPK-fertilizer from said phosphate salt containing fluorapatite .
  • the potassium salts are used, which are raw materials readily available on the market, in particular potassium chloride KCl.
  • As a nitrogen source ammonium nitrate NH4NO3 and ammonium sulphate (NH 4 ) 2 S0 4 are used. Ammonium sulfate is used as a stabilizing agent when using KCl as potassium source in the claimed NPK.
  • RU 2216526 discloses a method for obtaining a NPK-fertilizer with adjustable N:P 2 0 5 :K 2 0 ratio, said process comprising acid decomposition of phosphate raw material with nitric acid, adding nitrogen-containing component, neutralization with ammonia, mixing NP-slurry with potassium chloride and sulfate.
  • Patents RU 2439039 and RU 2223933 also disclose the processes of phosphate ore decomposition with nitric acid accompanied by neutralizing slurry with ammonia and adding potassium salts.
  • Patent RU 2107055 discloses a method for preparation of complex fertilizers by decomposition of phosphate rocks with a mixture of phosphoric and sulfuric acids with neutralization of the mixture with alkaline potassium salt such as potassium carbonate, followed by neutralization with ammonia.
  • the drawback of this process is the use of extraction phosphoric acid, which is an expensive product, the production thereof is accompanied by generation of a large amount of waste, namely phosphogypsum, also a lot of water is introduced into the system together with phosphoric acid, which necessitates evaporation stage to obtain the final product.
  • ammonia to neutralize the mixture reduces soluble phosphorus portion to less than 60%.
  • Chinese patent CN 1113900 (1994) discloses producing of a fertilizer containing nitrogen and phosphorus, wherein the fertilizer is produced from phosphate rock and nitric acid, and the resulting product is Ca(H 2 P0 4 ) 2 , which is crystallized, NH 4 H 2 P0 4 is obtained by mixing the ammonium nitrate with the mother liquor, and bubbling of the obtained mother liquor with ammonia yields CaHP0 4 .
  • the drawback of this process may include: the presence of evaporation stage in the process, in the product phosphorus is not in a water-soluble form of dicalcium phosphate, and the method of potassium introduction into fertilizer is not disclosed.
  • Patent GB 662079 discloses production of fertilizers containing soluble phosphorus salts based on the slurry resulting from decomposition of natural phosphates, DCP (dicalcium phosphate) or TCP (tricalcium phosphate) .
  • Phosphates are decomposed by sulfuric acid treatment, then the mixture is exposed to nitric acid to yield MAP and calcium nitrate.
  • the product is stabilized by adding ammonium sulfate, whereby gypsum and ammonium nitrate are formed from calcium nitrate. Additional quantity of added ammonium sulphate has a favorable effect on the fertilizer, as double salt of ammonium sulfate with two ammonium nitrate molecules is formed.
  • British patent GB 702 860 discloses the preparation of granulated NPK-fertilizers from raw material obtained from phosphate decomposition.
  • MCP monocalcium phosphate
  • the decomposition occurs in two steps.
  • One of the drawbacks of granulated complex NP-fertilizers according to the description is their plasticity. This problem was not solved in the production process.
  • Patent CN 1220236 discloses a method which comprises mixing of the hydrated lime with one or both substances: powdered Ca 3 (P0 4 ) 2 and CaHP0 4 , adding phosphoric acid with a concentration of 62% to 85% under stirring at 80°C for 20 to 60 seconds to give MCP (monocalcium phosphate) , followed by curing for 8-100 hours, natural drying and grinding to yield the product.
  • MCP monocalcium phosphate
  • H 3 P0 4 /Ca 3 ( P0 4 ) 2 or H 3 P0 /CaHP0 4 ratios are identical (7 to 16):100.
  • the powdered Ca(H 2 P0 4 ) 2 reacts with powdered Ca(OH) 2 to give CaHP0 4 and Ca (OH) 2 /Ca (H 2 P0 4 ) 2 ratio is (10 to 22): 100.
  • the drawbacks of this process include the use of hydrated lime, the production of which requires additional energy, the process is periodic (there is a product maturing stage) .
  • MCP Another methods for producing MCP are the processes of apatites decomposition with phosphoric acid.
  • Apatite reaction with phosphoric acid Apatite reaction with phosphoric acid:
  • Citride CN 1305946 discloses obtaining monocalcium phosphate (MCP) from phosphorite. This process includes reaction of phosphorite and sulfuric acid at temperatures ranging from 70°C to 95°C for 2-8 hours; filtration to obtain 10% to 30% phosphoric acid; adding CaC0 3 to phosphoric acid and removal of impurities; neutralization with Ca(OH) 2 and filtering; adding CaHP0 4 and CaO; and spray-drying to obtain Ca(H 2 P0 4 ) 2 and a product with a high phosphorus content (core of calcium salts of phosphoric acid, 19-22% phosphorus) .
  • a disadvantage of this process is that one of the process stages is the production of an aqueous phosphoric acid solution, therefore, the need of water evaporation leads to additional costs associated with carrying out the process.
  • the purified solution reacts with calcium hydroxide suspension to yield crystals suspension in DCP, which are then separated by decantation.
  • the resulting crystals are then reacted with acid ammonium sulfate to give monoammonium phosphate solution, and insoluble crystals of calcium sulfate dihydrate are separated by filtration .
  • concentrated hydrochloric acid and ammonia are added to DCP suspension. Filtration yields a solution with MCP concentration of more than 48%.
  • the drawbacks include: technological complexity of carrying out the process, the use of numerous reagents, product losses in precipitate during filtration and decantation, and also obtaining MCP in the form of a solution that complicates its further processing .
  • Mexican patent MX NL0500002 discloses a method for preparation of monocalcium phosphate MCP, sodium phosphate, potassium and MAP, where phosphate rock, sulfuric acid, calcium oxide, ammonium sulphate or potassium sulphate are used as starting materials.
  • the important part is the method for producing phosphate salts, which are prepared by reacting DCP (dicalcium phosphate) with appropriate acid sulphates of the corresponding (magnesium, ammonium, potassium) salts.
  • DCP diicalcium phosphate
  • appropriate acid sulphates of the corresponding (magnesium, ammonium, potassium) salts Upon gypsum filtration, the resulting MAP or other salts are concentrated in an evaporator and crystallized.
  • the disadvantage of the method is the stage of salts solution preparation and gypsum filtration, which leads to additional costs associated with product solidification by evaporation.
  • Using natural phosphate rock for decomposition results in a large quantities of waste — phosphogypsum.
  • MCP monocalcium phosphate
  • H3PO4 reaction of calcium containing compounds, such as lime milk
  • Another method includes preparation of calcium orthophosphate Ca 3 (P0 4 )2, known as calcium phosphate, by treating a mixture of calcium sulphate and phosphoric acid with sulfuric acid or by reaction of sulfuric acid with calcium sulfate and monocalcium phosphate Ca(H 2 P0 4 ) 2 mixture.
  • the NPK preparation is mainly carried out by decomposition of natural phosphates with acids.
  • the state of the art comprises a method for the preparation of a material which is simple superphosphate (SSP) or triple superphosphate (TSP) , by reaction of phosphates with sulfuric or phosphoric acid.
  • SSP simple superphosphate
  • TSP triple superphosphate
  • a soluble portion consists primarily of calcium monophosphate, and the insoluble part is gypsum in case of SSP (and other insoluble impurities in addition to those contained in the gypsum) .
  • feedstock is granulated in drum granulators with the addition of a small amount of alkali (e.g. ammonia).
  • alkali e.g. ammonia
  • Free phosphoric acid content which is up to 5% in the powdered superphosphate, is reduced by 1-2% due to neutralization in the process of granulation.
  • a water soluble portion is reduced reaching the level of 60% in such processes .
  • the present invention is aimed to develop a novel type of complex NPK-fertilizer having high water solubility of P 2 0 5 .
  • NPK-fertilizer using potassium chloride KC1 as a potassium source and ammonium nitrate as a nitrogen source in the presence of MCP (monocalcium phosphate) and gypsum.
  • the final product comprises anhydrous fine gypsum (calcium sulfate) providing access (for plants) to such element as sulfur, which is necessary and which is present in the target fertilizer introduced into the soil.
  • anhydrous fine gypsum calcium sulfate
  • the present invention provides improvement of NPK-fertilizer properties, while a method for its production can improve the strength of granules, allows to solve the problem associated with plasticity of granulated complex fertilizers and thereby enhance consumer properties of NPK-fertilizers .
  • the solution of the problem results in high efficiency of the product obtained, reducing the cost of the final product and significant expansion of the raw materials base.
  • the present invention provides complex nitrogen-phosphorus-potassium fertilizer (NPK) containing ammonium nitrate, monoammonium phosphate, anhydrous calcium sulfate, potassium nitrate, ammonium chloride, wherein mass fraction of total nitrogen is from 13-15%, mass fraction of total phosphates, in terms of P 2 0 5 , is from 11-15%, mass fraction of potassium, in terms of K 2 0, is from 7-8%.
  • NPK complex nitrogen-phosphorus-potassium fertilizer
  • the process for preparing a complex NPK-fertilizer from a solid phosphate salt includes decomposing of said solid phosphate salt with sulfuric acid according to semi-dry method, adding potassium chloride as a potassium source, ammonium nitrate as a nitrogen source, preparing NPK slurry, and granulating and drying the final product .
  • This solid phosphate salt is a mixture of fluorapatite Ca 5 (P0 4 ) 3 F and dicalcium phosphate CaHP0 4 x nH 2 0, where n is 0 to 2, with fluorapatite Ca 5 (P0 4 ) 3 F content from 27% to 99%.
  • the technical result of practicing this process is that water soluble form of P 2 0 5 reaches 98%. In other words, the phosphorus contained in the fertilizer is 98% water soluble.
  • An important point of resolving the technical problem is the fact that practicing said technological process results in obtaining MCP (monocalcium phosphate) by reaction in the form of monohydrate (i.e. it remained stable) .
  • the temperature during dicalcium phosphate decomposition should not exceed 120°C. At this temperature dehydration begins.
  • the process for producing involves the use of MCP in monohydrate form at the temperature not exceeding 120°C, which in turn avoids degradation of MCP to dicalcium phosphate and phosphoric acid.
  • sulphates particularly ammonium sulphate
  • sulphates enables to convert MCP to monoammonium phosphate in order to avoid the presence of residual reactive MCP in the final product, which solves the problem of NPK components decomposition with HC1 release during storage, and also to avoid problems with plasticity at granulation stage.
  • Another important aspect of the claimed process realization is adding sulfates to MCP, which provides anhydrous gypsum in certain process conditions. Namely, reaction of MCP with sulfates at the temperature not lower than 120°C provides substantially anhydrous gypsum.
  • Technological conditions for obtaining anhydrous gypsum in fine-dispersed form further ensure availability of essential fertilizer element, sulfur, upon fertilizer application in the soil .
  • the conditions of the proposed process namely that the temperature of the slurry obtained after preparing MCP and feeding to the reactor should not be less than 120°C, allow to avoid the formation of gypsum hemihydrate (which is highly undesirable for the resulting fertilizer) .
  • the present invention resolves the problem associated with the plasticity of granulated complex NPK-fertilizer .
  • MCP monocalcium phosphate
  • DCP as a starting material, is not a pure substance but rather a mixture, where, along with DCP, at least fluorapatite is present.
  • reaction enthalpy refers to the following general equation:
  • DCP is commonly referred to as "brushite", which is dicalcium phosphate dihydrate. According to the results of RTG measurements of the provided sample DCP, it is present in an anhydrous form “monetite”, therefore in equation (1) DCP is shown in anhydrous form. In accordance with RTG record after MCP preparation reaction, the resulting gypsum is in the form of anhydride and the reaction is exothermic.
  • reaction 1 MCP formation— proceeds in two stages :
  • sulfuric acid reacts with fluorapatite .
  • MCP water-soluble phosphorus
  • a system comprising MCP, ammonium nitrate and potassium chloride is unstable due to reaction of MCP and KC1 and the formation of ammonium nitrate and MCP intermediate . To avoid these reactions and to stabilize the quality of the final product it is necessary to remove reactive MCP from the system. This is achieved by reaction with sulphates, in specific embodiment, using ammonium sulfate with further formation of gypsum and monoammonium phosphate. Ammonium sulfate is dosed equimolarly with respect to the resultant MCP in the system:
  • NPK product prepared using DCP, sulfuric acid, ammonium nitrate and KC1 mainly comprises the following components:
  • the technological process for producing the claimed NPK-fertilizer according to the invention comprises the following steps :
  • phosphate salt in particular the mixture of DCP and fluorapatite
  • MCP monocalcium phosphate
  • a further scheme of the process is as follows: in the first reactor: fine-grained ammonium sulfate is fed, MCP reacts with ammonium sulfate to give gypsum and monoammonium phosphate . in the second reactor: ammonium nitrate is fed. Ammonium nitrate is dosed in the form of melt or granules through the dosing device . in the third reactor: finely crystalline potassium chloride is fed to complete the reaction.
  • a slurry is fed to granulation step, which is carried out in the granulator of suitable design by agglomeration and layering in a fluidized bed. Returns are input to the front part of the granulator. Drying is carried out with hot air. After carrying out the following operations: screening, crushing, cooling, surface treatment with anti-caking additive, the finished product suitable for storage and transportation is obtained.
  • Waste gases containing dust of products and raw materials used in the production as well as gases released during production are captured in wet scrubbers with the addition of neutralizing agents into absorbent .
  • the main object of the present invention is the production of NPK-fertilizer using KCl as a potassium source and ammonium nitrate as a nitrogen source in the presence of MCP and gypsum. Due to strict requirements concerning P2O5 water solubility it is necessary to have essentially all the phosphorus feedstock in the form of MCP or other salt of phosphoric acid, which would provide water-solubility. MCP should remain stable in order to prevent its conversion to DCP and phosphoric acid.
  • the whole proposed NPK production process can be divided into 2 main stages: the process of producing a water-soluble phosphate salt and the process of producing complex fertilizers from this salt.
  • the production of complex NPK fertilizer consists of two main processes: wet (NPK slurry production) and dry (granulation, milling, screening and cooling of the finished product) processes.
  • Fig. 1 is a diagram of wet process to give NPK slurry using potassium chloride KC1 as a potassium source in the product.
  • the phosphate salt being a mixture of calcium phosphates with fluorapatite (stream 1) together with sulfuric acid (stream 2) are fed into the flow device (unit A) , which is a mixer with fast rotating blades and reaction mass maturing unit. Sulfuric acid is dosed in equimolar ratio to the phosphate salt.
  • the process results in the following chemical reactions in the reaction mass in unit A:
  • H 2 S0 4 + 2CaHP0 4 + H 2 0 Ca(H 2 P0 4 ) 2 + CaS0 4
  • reaction of phosphate with sulfuric acid and phosphoric acid release the reaction of phosphoric acid with phosphate salt to give monocalcium phosphate (MCP) .
  • MCP monocalcium phosphate
  • the reaction of MCP formation may occur not completely, in particular, due to MCP decomposition in the presence of water.
  • Reactions 1 and 2 are exothermic, especially the reaction 2.
  • the technical solution for removing heat of reaction is a complex one: reactor is equipped with a water jacket and also part of the heat is removed from the system with exhaust gases and part of the heat is removed with water vapor. To ensure the removal of vapor and gases mixing unit A is operated under vacuum. Heat removal system parameters must be adjusted so that the temperature of the reaction mixture does not exceed 120°C.
  • the reaction mixture is fed into maturing unit, being a part of unit A, which is a device with a stirrer.
  • the following processes take place in the maturing unit: completion of the reaction processes; final removal of gases from the reaction mixture; averaging of the chemical and physical properties of the reaction mass.
  • the first slurry reactor (unit B) The first slurry reactor (unit B) :
  • MAP monoammonium phosphate
  • crystalline ammonium sulfate stream 5
  • a system comprising MCP, ammonium nitrate and potassium chloride is unstable due to reaction of MCP and KC1 and the formation of ammonium nitrate and MCP intermediate. To avoid these reactions and to stabilize the quality of the final product it is necessary to remove reactive MCP from the system by reaction with sulphates, in specific embodiment, using ammonium sulfate with further formation of gypsum and monoammonium phosphate.
  • reaction mass (stream 6) containing monoammonium phosphate and gypsum enters the next reactor via overflow
  • the main agent of the process in the reactor is ammonium nitrate. It is supplied in granulated form. Two approaches can be used to input it into the system:
  • ammonium nitrate Prior to inputting to the system ammonium nitrate is melted in a separate reactor to give melt, then aqueous solution containing 93-97% ammonium nitrate at about 158 °C is dosed into the slurry reactor .
  • Ammonium nitrate is input into the system in the form of granules, which are dosed into the slurry reactor using a dosing device .
  • Ammonium nitrate in the form of granules or melt (stream 7), depending on the product composition, is fed into the reactor unit C.
  • the reactor mixture is maintained at a temperature not exceeding 160°C.
  • the heat is transferred by steam jacket and direct steam. No chemical processes take place in the reactor, the mixing gives homogeneous slurry in the saturated ammonium nitrate solution.
  • Hydrogen fluoride is captured in unit F.
  • the stream of vapor and low pressure gases from the mixer (stream 3) is fed to the absorption column, where hydrogen fluoride is captured using the main solution (slurry of calcium carbonate or calcium hydroxide) .
  • the end product, calcium fluoride is filtered, washed and, according to the application, is either recycled or dried and packaged and then sent to a warehouse.
  • NPK product prepared using phosphate salt, sulfuric acid, ammonium nitrate, ammonium sulphate and potassium chloride mainly comprises the following components:
  • Slurry at the temperature 125°C to 145°C flows by gravity from the third reactor to the granulator of paddle mixer type. Returns are input to its front part.
  • Distributor distributes slurry in the material within the granulator.
  • Granulation is carried out by agglomeration and layering in a fluidized bed, which is created by blades mounted on two shafts.
  • Steam with pressure 0,3 to 0,4 Pa may be fed to granulator to adjust the optimal operating conditions of the granulator (temperature, humidity) according to the quality of the combined fertilizer produced.
  • NPK nitrogen-phosphorus-potassium fertilizer
  • the production of the above NPK based on solid phosphate salt being a mixture of fluorapatite Ca 5 (PO4) 3F and dicalcium phosphate CaHP0 4 x nH 2 0, where n is 0 to 2, with fluorapatite Ca 5 (P0 4 ) 3 F content from 27% to 99%, allows the use of potassium chloride and ammonium nitrate.
  • phosphate salt As raw material phosphate salt is used, said salt is obtained by decomposition of phosphoric rock with hydrochloric acid, separating the insoluble precipitate, followed by precipitation of solid phosphate salt using calcium carbonate slurry.
  • the rock from Keysik deposits was used: Substance Unit Content
  • Fluorine contained in the phosphate salt and obtained by decomposition of phosphate ore with hydrochloric acid is present in the mixture in the form of fluorapatite, which is confirmed by analytical control of the samples.
  • Phosphate salt DCP containing 27% fluorapatite is further used for NPK production.
  • the stage of decomposition of said solid phosphate salt with sulfuric acid is carried out at the temperature 110°C to 120°C using semi-dry method, where decomposition takes place with low water content. This necessary condition is due to the selection of equimolar ratios in the system to maintain stability of MCP in monohydrate form.
  • ammonium sulphate [224 kg/h] is fed in the form of fine powder, the process is carried out at a temperature of 130°C to ensure the conditions for anhydrous gypsum formation.
  • Ammonium nitrate melt [726 kg/h] is fed to the second reactor, the process is carried out in the reactor at 160°C.
  • Fine-grained potassium chloride [320 kg/h] is fed to the third reactor, the reaction in the third reactor occurs rapidly and completes at 120°C.
  • the basic process used is described above with reference to the scheme in Fig. 1.
  • the resulting complex nitrogen-phosphorus-potassium fertilizer (NPK) contains ammonium nitrate, monoammonium phosphate , anhydrous calcium sulfate, potassium nitrate, ammonium chloride, wherein mass fraction of total nitrogen is from 13-15%, mass fraction of total phosphates, in terms of P2O5, is from 11-15%, mass fraction of potassium, in terms of K2O, is from 7-8%.
  • the production of the above NPK based on solid phosphate salt being a mixture of fluorapatite Ca 5 (P0 4 ) 3 F and dicalcium phosphate CaHP0 4 x nH 2 0, where n is 0 to 2, with fluorapatite Ca 5 (P0 4 ) 3 F content from 27% to 99%, allows the use of potassium chloride and ammonium nitrate.
  • phosphate salt As raw material phosphate salt is used, said salt is obtained by decomposition of phosphoric rock with hydrochloric acid, separating the insoluble precipitate, followed by precipitation of solid phosphate salt using calcium carbonate slurry. Similar to Example 1, for the production of the phosphate salt the rock from Keysik deposits was used:
  • Fluorine contained in the phosphate salt and obtained by decomposition of phosphate rock with hydrochloric acid is present in the mixture in the form of fluorapatite, which is confirmed by analytical control of the samples.
  • Phosphate salt DCP containing 99% fluorapatite is further used for NPK production:
  • stage of decomposition of said solid phosphate salt with sulfuric acid is carried out at the temperature 110°C to 120°C using semi-dry method, where decomposition takes place with low water content. This necessary condition is due to the selection of equimolar ratios in the system to maintain stability of MCP in monohydrate form.
  • ammonium sulphate [224 kg/h] is fed in the form of fine powder, the process is carried out at a temperature of 130°C to ensure the conditions for anhydrous gypsum formation.
  • Ammonium nitrate melt [726 kg/h] is fed to the second reactor, the process is carried out in the reactor at 160°C.
  • Fine-grained potassium chloride [320 kg/h] is fed to the third reactor, the reaction in the third reactor occurs rapidly and completes at 120°C.
  • the production of the above NPK based on solid phosphate salt being a mixture of fluorapatite Ca 5 (P0 4 ) 3 F and dicalcium phosphate CaHP0 4 x nH 2 0, where n is 0 to 2, with fluorapatite Ca 5 (P0 4 ) 3 F content from 27% to 99%, allows the use of potassium chloride and ammonium nitrate.
  • raw material phosphate salt As raw material phosphate salt is used, said salt is obtained by decomposition of phosphoric rock with hydrochloric acids similar to Examples 1 and 2.
  • the resulting complex nitrogen-phosphorus-potassium fertilizer contains ammonium nitrate, monoammonium phosphate, anhydrous calcium sulfate, potassium nitrate, ammonium chloride, wherein mass fraction of total nitrogen is 13-14%, mass fraction of total phosphates, in terms of P 2 0 5 , is from 12-13%, mass fraction of potassium, in terms of K 2 0, is from 7-8%.

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Abstract

La présente invention concerne un engrais NPK, azote-phosphore-potassium, complexe, dans lequel la fraction massique de l'azote total est comprise entre 13 et 15 %, la fraction massique des phosphates totaux, en termes de P2O5, est comprise entre 11 et 15 %, la fraction massique de potassium, en termes de K2O, est comprise entre 7 et 8 %, ainsi qu'un procédé de préparation dudit engrais à partir d'un sel de phosphate solide, qui est un mélange de fluorapatite Ca5(PO4)3F et de phosphate dicalcique CaHPO4nH2O, n étant compris entre 0 et 2, avec une teneur en fluorapatite Cas(PO4)3F comprise entre 27 % et 99 %, en utilisant divers sels de potassium, en particulier du chlorure de potassium, et sels d'ammonium, en tant que sources de nutriments dans l'engrais. Le résultat technique est de conférer des propriétés améliorées d'engrais NPK, en particulier un procédé pour sa préparation permet d'améliorer la robustesse des granules, pour résoudre le problème lié à la plasticité des engrais complexes granulés, d'améliorer la solubilité dans l'eau du phosphore contenu dans l'engrais de 98 %, ce qui améliore les propriétés de consommation de l'engrais NPK.
PCT/RU2017/000108 2016-03-03 2017-03-01 Engrais npk contenant du phosphore, du potassium et de l'azote et procédé de préparation d'un engrais npk contenant du phosphore, du potassium et de l'azote granulé WO2017151017A1 (fr)

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CN201780005551.9A CN108473380A (zh) 2016-03-03 2017-03-01 含有磷钾氮的npk肥料及用于制备粒化的含有磷钾氮的npk肥料的方法

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RU2016107776A RU2626947C1 (ru) 2016-03-03 2016-03-03 Фосфоркалийазотсодержащее npk-удобрение и способ получения гранулированного фосфоркалийазотсодержащего npk-удобрения
RU2016107776 2016-03-03

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EP4317119A1 (fr) * 2022-08-04 2024-02-07 SABIC Global Technologies B.V. Engrais complexe contenant de l'azote, du phosphore et du soufre encapsulés dans des nutriments de calcium et de magnésium secondaire

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EP3394007A1 (fr) * 2015-12-21 2018-10-31 Yara International ASA Composition d'engrais à base de nitrate d'ammonium, et son procédé de fabrication
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