WO2017143415A1 - Method for producing phosphate fertilizers from phosphate rock with a low p2o5 content and use of triple superphosphate or dregs from the production of phosphoric acid - Google Patents
Method for producing phosphate fertilizers from phosphate rock with a low p2o5 content and use of triple superphosphate or dregs from the production of phosphoric acid Download PDFInfo
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- WO2017143415A1 WO2017143415A1 PCT/BR2016/050041 BR2016050041W WO2017143415A1 WO 2017143415 A1 WO2017143415 A1 WO 2017143415A1 BR 2016050041 W BR2016050041 W BR 2016050041W WO 2017143415 A1 WO2017143415 A1 WO 2017143415A1
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- WO
- WIPO (PCT)
- Prior art keywords
- production
- phosphate
- fertilizers according
- phosphate fertilizers
- phosphoric acid
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B13/00—Fertilisers produced by pyrogenic processes from phosphatic materials
- C05B13/02—Fertilisers produced by pyrogenic processes from phosphatic materials from rock phosphates
Definitions
- the present invention relates to a process of producing phosphate fertilizers through the use of triple superphosphate marketed in bulk or sludge from the manufacture of phosphoric acid for the enrichment of P2O5 poor phosphate rocks and obtaining a more practical and efficient phosphate fertilizer. .
- thermophosphate manufactured by electrofusion of phosphate rocks in combination with S1O2 and MgO balancing, by the addition of oxides during fusion.
- WO 2007/132497 describes fertilizer compounds having a glass matrix having a mass composition of phosphorus (as P2O5) in the 2-45% range of potassium (as K 2 O) in the 2-45% range, of other secondary nutrients (calcium, magnesium, sulfur and, if necessary, sodium) and trace elements.
- the production method of this fertilizer compound comprises mixing a plurality of precursors of chemical compounds comprised in the final fertilizer, in powder or pellet state. These precursors include kaolinite, zinc oxide, potassium feldspar, iron carbonate, potassium carbonate, calcium carbonate, colemanite, dolomite, molybdenum oxide, mono ammonium phosphate, among others.
- Document PM 106717-9 relates to the production and use of a weak acid soluble phosphorus potassium fertilizer, which is produced by a process of melting the raw materials followed by rapid cooling which provides the formation of a glassy and amorphous material. containing weak acid soluble phosphorus and potassium phases.
- a weak acid soluble phosphorus potassium fertilizer which is produced by a process of melting the raw materials followed by rapid cooling which provides the formation of a glassy and amorphous material. containing weak acid soluble phosphorus and potassium phases.
- superphosphates and triplophosphates are also used as fertilizers, but their use contributes to an excessive acidification of the soil, requiring the use of increasing amounts of ground limestone used in an additional operation called "liming".
- the neutralizing power of super and triplophosphates is zero.
- PM 106717-9 uses the mixture of alkaline rock, apatite and phosphorite, as well as raw materials rich in silicon oxides and rich in magnesia, such as calcined or sintered magnesite, calcined dolomite, among other materials.
- the main P2O5-containing natural raw materials used in the manufacture of the above listed fertilizers are apatites and phosphorites. Originally these minerals had P2O5 contents ranging from 18% to 40% by mass based on the total mass of the mineral. Today, phosphorus mineral deposits with these levels are increasingly rare, with only 5% by weight of P2O5 based on the total mass of the mineral, or even less.
- the mineral used has an average content lower than 25% by weight of P2O5 based on the total mass of the mineral, which needs to be improved and this is done systematically by sieving, separating the fines, increasing this content.
- approximately 28 to 30 wt.% of P2O5 based on the total mass of the mineral is desirable.
- the fines of this particle size separation have very low contents which, to be used directly, would require the use of ores with more than 30 mass% of P2O5, which are excessively expensive.
- a solution for using these fines would be in admixture with products with maximum P2O5 contents, such as bulk triple superphosphate, with 44 to 50% by weight of P2O5, or a sludge from phosphoric acid manufacture with approximately 28 to 57% by weight. P2O5 mass.
- P2O5 contents such as bulk triple superphosphate, with 44 to 50% by weight of P2O5, or a sludge from phosphoric acid manufacture with approximately 28 to 57% by weight. P2O5 mass.
- the present invention relates to a process for producing phosphate fertilizers comprising the steps of: a) mixing low P2O5 phosphate rock and triple superphosphate marketed in bulk from the manufacture of phosphoric acid; b) melting the material obtained in (a); and c) cooling the melt obtained from step (b).
- the invention further relates to the use of triple superphosphate sold in bulk or sludge from the manufacture of phosphoric acid in admixture with P2O5 poor phosphate rocks for enrichment thereof and to obtain an alkaline pH phosphate fertilizer.
- the process for producing phosphate fertilizers of the invention comprises the steps of: (a) mixing low P2O5 phosphate rock and triple superphosphate sold in bulk or sludge from manufacture phosphoric acid; (b) melting the material obtained in (a); and (c) cooling the melt obtained from step (b).
- the phosphate rocks used in step (a) are ground and classified below the 100 mesh (150 mm) mesh, having approximately 17% to 25% P2O5 mass based on total mass of phosphate rocks. In addition, these rocks can have up to 25% Fe 2 03 mass based on the total mass of phosphate rocks.
- the phosphoric acid sludge used in the process of the invention has approximately 28% to 57% by weight of P2O5, based on the total sludge mass. Such sludge is in liquid form and is applied by spraying in step (a) of the process of the invention.
- Phosphoric acid sludge is produced by the wet process by reaction of sulfuric acid with phosphate rock. In acidulation of phosphate rock, less sulfuric acid is used.
- triple superphosphate used has approximately 44% to 50% by weight of P2O5, based on the total mass of triple superphosphate sold in bulk.
- Triple superphosphate is obtained by reacting phosphate rock with 50% phosphoric acid. In its production the crushed rock is sent to the dosing scale, later sent to the mixer, where 50% phosphoric acid is added, initiating the reaction. This pulp-like mixture flows continuously into a reaction belt, where an exothermic reaction occurs, releasing gases and particulate matter. As a result of this reaction, the pulp becomes a solid product with high porosity and low specific weight. At the end of the reaction belt the superphosphate layer formed is broken by a disintegrator. The final product is taken to the cure warehouse where the reaction will complement each other.
- step (b) After the curing period is sold in bulk.
- briquetting is performed, and after briquetting the material obtained is dried in rotary dryers and sieved.
- Such screening is performed on 200 mesh (75 mm) mesh, where the fraction finer than 200 mesh (75 mm) returns to step (a), while the thicker than 200 mesh (75 mm) is ensiled to proceed to step (b).
- an acidic pH material is obtained. from approximately 3.0 to 4.0.
- the acidic pH material proceeds to the melting process.
- the fusion is performed in electric arc furnaces, continuously poured directly into water (quenching).
- the temperature in the ovens is from 1200 to 1600 ⁇ , preferably 1400 ⁇ .
- step (c) After melting, the melt in the above condition is immediately cooled with large amounts of water (quenching) (step (c)), solidifying into amorphous / vitreous granules in a wide range below 850 micrometres.
- the water / molten mass ratio is 5 to 10/1.
- the amorphous / vitreous granules obtained are already alkaline phosphate fertilizers with a pH greater than or equal to 9.
- the obtained fertilizer has a content of 18% or greater by mass of total P2O5 based on the total mass of the fertilizer.
- Phosphate fertilizer is obtained as a granulated product, and the granulated product plus cooling water is sent to a settling tank for separation. After separation the cooling water returns to the process and the granulated fertilizer is stored.
- the fertilizer is a fused thermophosphate fertilizer.
- the invention also relates to the use of bulk commercially available triple superphosphate or sludge from phosphoric acid manufacture in admixture with P2O5 poor phosphate rocks for enrichment and obtaining an alkaline pH phosphate fertilizer by the process described above. .
- the process starts from an already ground, low-grade, P2O5-graded phosphate rock to which is added thin, more economical bulk triple superphosphate, plus water, directly into a briquette machine and thereafter. directly to a rotary dryer.
- the dried briquettes pass through a sieve to remove the fines, which return to the mixing and briquetting process again, and the retained ones, which are reserved for melting in electric arc furnaces.
- the melt is continuously poured into water for abrupt cooling, granulating the solidified melt.
- the granulated product plus cooling water mixture is pumped into a settling tank, separating the return water from the process and the amorphous granulate which is the desired product.
- a natural ground phosphate rock, classified below the 100 mesh (150 mm) mesh, with approximately 20% by weight of P2O5 is transferred to a mixer together with a thin, approximately triple bulk commercial superphosphate. 44% to 50% by weight of P2O5, plus sufficient water for proper briquetting consistency.
- the mixture thus obtained should contain approximately 28% by weight of P2O5 (dry basis).
- the material is dried. in rotary dryers and are sieved over 200 mesh. The fraction finer than 200 mesh (75 mm) returns to the previous mixing and briquetting process while the thicker than 200 mesh (75 mm) is ensiled, waiting to enter the melting furnaces or, if necessary, follow directly to the melting furnaces.
- the fine bulk triple superphosphate may be replaced by phosphoric acid sludge with approximately 28 to 57 mass% of P2O5 and use small amount of hydrated lime [Ca (OH) 2 ] to accelerate the reaction of components with respective temperature increase and water evaporation.
- phosphoric acid sludge with approximately 28 to 57 mass% of P2O5 and use small amount of hydrated lime [Ca (OH) 2 ] to accelerate the reaction of components with respective temperature increase and water evaporation.
- Ca (OH) 2 hydrated lime
- phosphoric acid sludge containing approximately 28 to 57% by weight of P2O5 can be employed which, as it is in liquid form, is applied by spraying.
- the poor rock is placed inside a continuous rotary mixer, where the sludge of phosphoric acid that reacts with each other instantly sprays.
- thermophosphate manufacturing process of the present invention since the initial mixture (feedstock oven) will be melted, liquefied with subsequent cooling in water.
- the final characteristic of the melt thermophosphate fertilizer is not modified, maintaining all inherent properties of the marketed product as well as a desired pH> 9.
- Average (2) Average calcined base content Table II - Typical analysis of triple superphosphate (TSP) sold at ranch:
- Average (2) Average calcined base content
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- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/BR2016/050041 WO2017143415A1 (en) | 2016-02-25 | 2016-02-25 | Method for producing phosphate fertilizers from phosphate rock with a low p2o5 content and use of triple superphosphate or dregs from the production of phosphoric acid |
BR112018017306-1A BR112018017306B1 (en) | 2016-02-25 | 2016-02-25 | PROCESS FOR THE PRODUCTION OF PHOSPHATE FERTILIZERS FROM POOR PHOSPHATE ROCKS IN P2O5 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/BR2016/050041 WO2017143415A1 (en) | 2016-02-25 | 2016-02-25 | Method for producing phosphate fertilizers from phosphate rock with a low p2o5 content and use of triple superphosphate or dregs from the production of phosphoric acid |
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WO2017143415A1 true WO2017143415A1 (en) | 2017-08-31 |
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PCT/BR2016/050041 WO2017143415A1 (en) | 2016-02-25 | 2016-02-25 | Method for producing phosphate fertilizers from phosphate rock with a low p2o5 content and use of triple superphosphate or dregs from the production of phosphoric acid |
Country Status (2)
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BR (1) | BR112018017306B1 (en) |
WO (1) | WO2017143415A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1406813A (en) * | 1971-09-10 | 1975-09-17 | Occidental Petroleum Corp | Production of potassium polyphosphates from phosphate acid sludges |
JPH02267178A (en) * | 1989-04-05 | 1990-10-31 | Minamikiyuushiyuu Kagaku Kogyo Kk | Fused phosphate fertilizer and preparation thereof |
CN1066051A (en) * | 1991-04-25 | 1992-11-11 | 李江华 | The method for making of active superphosphate fertilizer |
-
2016
- 2016-02-25 WO PCT/BR2016/050041 patent/WO2017143415A1/en active Application Filing
- 2016-02-25 BR BR112018017306-1A patent/BR112018017306B1/en active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1406813A (en) * | 1971-09-10 | 1975-09-17 | Occidental Petroleum Corp | Production of potassium polyphosphates from phosphate acid sludges |
JPH02267178A (en) * | 1989-04-05 | 1990-10-31 | Minamikiyuushiyuu Kagaku Kogyo Kk | Fused phosphate fertilizer and preparation thereof |
CN1066051A (en) * | 1991-04-25 | 1992-11-11 | 李江华 | The method for making of active superphosphate fertilizer |
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BR112018017306A2 (en) | 2019-01-02 |
BR112018017306B1 (en) | 2023-03-28 |
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