CN108602673B - Device for the joint production of phosphate and potassium sulphate - Google Patents
Device for the joint production of phosphate and potassium sulphate Download PDFInfo
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- CN108602673B CN108602673B CN201780009438.8A CN201780009438A CN108602673B CN 108602673 B CN108602673 B CN 108602673B CN 201780009438 A CN201780009438 A CN 201780009438A CN 108602673 B CN108602673 B CN 108602673B
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- phosphate
- hydrochloric acid
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- leaching
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 128
- 239000010452 phosphate Substances 0.000 title claims abstract description 123
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 31
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 31
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 31
- 239000001120 potassium sulphate Substances 0.000 title claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 183
- 238000002386 leaching Methods 0.000 claims abstract description 54
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 44
- 239000007791 liquid phase Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007790 solid phase Substances 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 235000019739 Dicalciumphosphate Nutrition 0.000 claims abstract description 10
- 229910000390 dicalcium phosphate Inorganic materials 0.000 claims abstract description 10
- 229940038472 dicalcium phosphate Drugs 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 9
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 9
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019731 tricalcium phosphate Nutrition 0.000 claims abstract description 7
- 229940078499 tricalcium phosphate Drugs 0.000 claims abstract description 7
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 5
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 claims abstract 3
- 238000005406 washing Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 8
- 239000010808 liquid waste Substances 0.000 claims description 5
- 239000002910 solid waste Substances 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 2
- 229940077441 fluorapatite Drugs 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 abstract description 110
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005201 scrubbing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 25
- 239000002002 slurry Substances 0.000 description 11
- 239000003337 fertilizer Substances 0.000 description 9
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000712 assembly Effects 0.000 description 3
- 238000000429 assembly Methods 0.000 description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000150 monocalcium phosphate Inorganic materials 0.000 description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000002374 bone meal Substances 0.000 description 2
- 229940036811 bone meal Drugs 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/01—Treating phosphate ores or other raw phosphate materials to obtain phosphorus or phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
Abstract
The present invention relates to the field of chemical technology and more particularly to a plant for the joint production of phosphates such as dicalcium phosphate and/or tricalcium phosphate and potassium sulphate, said plant comprising a unit for the production of potassium sulphate and hydrochloric acid from potassium chloride and sulphuric acid, which comprises a furnace for the production of potassium sulphate, a plant for the production of hydrochloric acid from exhaust gases and an assembly for the preparation of hydrochloric acid for leaching, and a unit for the production of phosphates from phosphate raw materials, which comprises a hydrochloric acid leaching assembly and a plant for the preparation of a solution for neutralization, which is connected to a liquid phase neutralization and phosphate precipitation assembly by a main conduit, downstream of which the following are arranged in series, connected by a transfer conduit: a phosphate separation filter, a phosphate scrubbing module and a phosphate drying module, wherein the module for separating the solid and liquid phases after leaching is arranged between the hydrochloric acid leaching module and the liquid phase neutralization and phosphate precipitation module and is connected thereto by a main conduit, and the furnace for the production of potassium sulphate is connected by a conduit via a gas outlet to the module for the production of hydrochloric acid from the exhaust gases, which is connected by a conduit via a module for the preparation of hydrochloric acid for leaching to the hydrochloric acid leaching module.
Description
Technical Field
The present invention relates to the field of chemical technology and more particularly to a device for the joint production of phosphates such as dicalcium phosphate and/or tricalcium phosphate and potassium sulfate.
Background
Phosphate and potassium sulfate are widely demanded by modern fertilizer markets. The former is used to produce various phosphorus fertilizer products, while the potassium sulfate itself is a chlorine-free potassium fertilizer. This is why the development of efficient and cost-effective equipment for its production is a highly relevant problem in current chemical technology.
There is a considerable body of literature known to produce phosphate by the decomposition of phosphate ore using hydrochloric acid. For example, the inventor's certificate SU1470663 discloses the production of dicalcium phosphate as a result of: decomposition of 35% hydrochloric acid of the phosphate raw material in an aqueous suspension at a temperature of 35-40 ℃ using a hydrochloric acid feed rate of 0.24-0.60kg/h/100g apatite. Documents SU842083 and SU994457 disclose the production of complex fertilizers from phosphate raw materials by their hydrochloric acid decomposition, which decomposition involves the use of dilute hydrochloric acid (1-4%). However, none of the documents teach or suggest the source of hydrochloric acid and the equipment used in the production process.
The closest to the present invention is an apparatus for producing phosphate, which includes a hydrochloric acid leaching module, a device for preparing a solution for neutralization, a liquid phase neutralization and phosphate precipitation module, a phosphate separation filter, a phosphate washing module and a phosphate drying device (see Dzhafarov I.Ph. Precision production. Moscow, publishing House "Food Industry",1975, p.5-57). Known is a plant for producing dicalcium phosphate as a feed phosphate from crude bone meal by means of hydrochloric acid leaching. Whereas the hydrochloric acid leaching module is in the form of a reactor (steeping device), continuously combined to form a cascade (battery) or bank by co-current flow of hydrochloric acid and hydrochloric acid leaching products, and the liquid phase neutralization and phosphate precipitation module is made in the form of several reactors (precipitators) connected to each other in series to ensure continuity of the process and equipped with tanks for collecting and homogenizing the phosphate slurry formulation, the equipment for preparing the solution for neutralization is the equipment for preparing milk of lime, thus allowing good recycling of high quality phosphate raw material (coarse bone meal), excluding the use of additional devices for separating the solid and liquid phases in the leaching stage (semi-solid organic waste is removed from the reactors by vacuum suction). However, since such equipment is dispensed with during the feeding phase of phosphate ores, in particular of low quality ores, which are recycled, the solid leaching waste can block the reactor of the neutralization and phosphate precipitation unit and then the reactor of the product-phosphate itself. This limits the efficiency and field of use of the known device. Furthermore, in order to operate the plant, an external source of hydrochloric acid is required, which is the input hydrochloric acid, the required amount of which is not always available technically and logistically, the latter of which increases the cost of the phosphate production and limits its field of use.
Disclosure of Invention
This is why the object of the present invention is to provide an apparatus for the decomposition of phosphate raw materials which comprises the units for producing hydrochloric acid required for the process and which enables the simultaneous production of phosphate and potassium sulphate.
This object is achieved as a result of the development of a new plant for the joint production of phosphate and potassium sulphate, which plant comprises:
a unit for producing potassium sulphate and hydrochloric acid from potassium chloride and sulphuric acid, comprising a furnace for producing potassium sulphate, a plant for producing hydrochloric acid from exhaust gases and an assembly for preparing hydrochloric acid for leaching, and
a unit for producing phosphate from phosphate raw material, comprising a hydrochloric acid leaching module, a device for preparing a solution for neutralization connected to a liquid phase neutralization and phosphate precipitation module by a main conduit, downstream of which are the following in a continuous arrangement connected by a transfer pipe: a phosphate separating filter, a phosphate washing component and a phosphate drying device,
wherein the device for separating the solid and liquid phases after leaching is arranged between the hydrochloric acid leaching component and the liquid phase neutralization and phosphate precipitation component and is connected thereto by a main conduit, and the furnace for the production of potassium sulphate is connected by a conduit via a gas outlet to the device for the production of hydrochloric acid from the off-gas, which is connected by a conduit to the hydrochloric acid leaching component via the component for the preparation of hydrochloric acid for leaching.
The invention provides the basic technical effect that phosphate can be produced from phosphate raw materials of different qualities, which is ensured by an optimization of the production modes and conditions that are optimal for a given raw material, while at the same time producing the valuable mineral fertilizer potassium sulphate on the plant. In addition, the device according to the invention makes it possible to significantly reduce the transportation costs of raw materials and to optimize energy costs.
The plant according to the invention is designed for the production of the following phosphates: dicalcium phosphate, tricalcium phosphate and mixtures thereof, and mixtures of dicalcium phosphate, tricalcium phosphate and phosphate-containing minerals, for example with fluorapatite. Phosphate ore (apatite) containing more than 20% of phosphorus pentoxide is used for the production of phosphate. The plant according to the invention makes it possible to produce a commercial product (phosphate) which, when used in the hydrochloric acid leaching (phosphate ore decomposition) produced by the plant itself, is a dry phosphate. In the apparatus of the present invention, as a result of the production of hydrochloric acid using sulfuric acid, a valuable chlorine-free potassium fertilizer, potassium sulfate, is produced. The amount of hydrochloric acid required for leaching produced by the off-gas is directly proportional to the volume of potassium sulphate produced and the concentration of the hydrochloric acid can be as high as 33wt%, providing the opportunity to select the optimum leaching mode, and in particular the optimum concentration and acid consumption rate for most types of phosphate raw materials, depending on the type and quality of the phosphate raw material. A unit for the production of potassium sulphate and hydrochloric acid from potassium chloride and sulphuric acid, comprising a furnace for the production of potassium sulphate and an apparatus for the production of hydrochloric acid from off-gas, included in a plant, facilitating the implementation of the process for the manufacture of potassium sulphate within the plant and the production of hydrochloric acid for leaching in the plant; and the provision of a module for preparing hydrochloric acid for use in leaching in the plant facilitates the production of the required amount of hydrochloric acid with the desired optimum concentration of the raw material. The apparatus for preparing a solution for neutralization and the liquid phase neutralization and phosphate precipitation module installed in a unit for producing phosphate from a phosphate feedstock enable the production of a desired qualitative and quantitative formulation of phosphate in a phosphate product, as well as the apparatus for separating the solid and liquid phases after leaching. Among them, the equipment for separating solid and liquid phases after leaching, the phosphate separation filter, the phosphate washing module ensure high product purity, while the drying equipment completes the production of commercial phosphate. The device of the invention, with the composite of the characteristics described, ensures the production of commercial phosphates from raw materials with different qualitative and quantitative formulations, while at the same time ensuring continuity and high efficiency of the process.
Thus, unlike prior art solutions, the present invention for the first time proposes a plant for producing commercial phosphate from phosphate raw materials of different quality, which ensures, by optimizing the operating modes and conditions in terms of raw materials or end products, the leaching of the phosphate raw materials with the waste hydrochloric acid generated in the plant, and for the production of potassium sulfate, a new product and valuable product of such a plant. In addition to the production of hydrochloric acid, the plant of the invention uses sulfuric acid and potassium chloride, which are available and cheap raw materials, facilitating the implementation of said plant on an industrial scale.
Drawings
FIG. 1 is a schematic illustration of the construction and operation of a device according to the present invention.
Detailed Description
The plant for the production of phosphate and potassium sulphate comprises a unit B for the production of phosphate comprising a hydrochloric acid leaching assembly 4 with inlets for phosphate raw material and hydrochloric acid, a plant 5 for separating solid and liquid phases after leaching, a liquid phase neutralisation and phosphate precipitation assembly 6, a plant 7 for preparing a solution for use in neutralisation, a phosphate separation filter 8, a phosphate washing assembly 9, a phosphate drying apparatus 10, and a plant a for the production of potassium sulphate and hydrochloric acid comprising a furnace 1 for the production of potassium sulphate, a plant 2 for the production of hydrochloric acid from waste gas and a plant 3 for preparing hydrochloric acid for use in leaching. Wherein the outlet of the hydrochloric acid leaching module 4 is connected by piping to the inlet of the plant 5 for separating the solid and liquid phases after leaching, the outlet of the plant 5 for the solid phase is the outlet of the apparatus for solid waste, and its outlet for the liquid phase is connected by piping to the inlet of the leaching liquid phase of the unit 6 for feed liquid phase neutralization and phosphate precipitation, the inlet of the solution for neutralization of the unit 6 for liquid phase neutralization and phosphate precipitation is connected by piping to the outlet of the plant 7 for preparing the solution neutralized in use, the outlet of the liquid phase neutralization and phosphate precipitation module 6 is connected by piping to the inlet of the phosphate separating filter 8, its outlet is the outlet of the plant for liquid waste, and its outlet for phosphate is connected by piping to the phosphate drying plant 10 via the phosphate scrubbing module 9, the outlet of the plant 10 is the outlet of the apparatus for commercial products, the furnace 1 for potassium sulphate production has an inlet for potassium chloride and sulfuric acid and an outlet for the products, and the outlet of the furnace 1 for gases is connected by piping to the inlet of the plant 2 for producing hydrochloric acid from the waste gas, the plant 2 for producing hydrochloric acid also has an inlet for water and its inlet for preparing the leaching module for hydrochloric acid through the inlet of the leaching module 3, and the outlet is connected to the inlet of the second leaching module for preparing hydrochloric acid through the hydrochloric acid.
The apparatus operates as follows. The required amounts of potassium chloride and concentrated sulfuric acid are fed to a furnace 1, where potassium sulfate is produced as a result of the high-temperature reaction, and hot gases containing gaseous hydrogen chloride are removed from the furnace via a conveying pipe into a plant 2 for producing hydrochloric acid from the exhaust gases. In the apparatus 2, the gas is cooled and the hydrogen chloride is absorbed by the water fed to the apparatus 2 and accumulates in the apparatus 2 in the form of hydrochloric acid. When the off-gas hydrochloric acid concentration is high, the acid is pumped via a pipe to the module 3 for preparing hydrochloric acid for leaching. In the module 3, the hydrochloric acid is diluted to obtain a predetermined concentration, and the hydrochloric acid having the predetermined concentration is accumulated in an amount required for plant operation. Meanwhile, in the apparatus 7 for preparing a solution for neutralization, a neutralizing agent is mixed with water to obtain a solution for neutralization (milk of lime, calcium carbonate suspension, etc.) having a predetermined concentration.
The required amount of phosphate raw material is fed to the hydrochloric acid leaching unit 4 in the required degree of dispersion, for example in the form of ground phosphate rock, wherein hydrochloric acid is simultaneously fed therein in the required concentration and in the required amount from the module 3. In the module 4, the phosphate is transferred into solution by the action of hydrochloric acid, while at the outlet a slurry is formed which mainly comprises monocalcium phosphate, soluble metal chlorides and solid impurities. The slurry transferred from the module 4 to the device 5 for separating solid and liquid phases after leaching is separated into a solid phase in the form of solid waste removable by the apparatus and a liquid phase in the form of an acid solution, wherein the liquid phase mainly comprises monocalcium phosphate and soluble impurities. The acid solution of phosphate and soluble impurities entering the neutralization and phosphate precipitation assembly 6 is mixed with the solution for neutralization delivered in the required amount from the apparatus for preparing a solution for neutralization 7, the monocalcium phosphate being converted into dicalcium phosphate (and even tricalcium phosphate or phosphate mixture in the appropriate mode chosen) which precipitates when the pH of the mixture increases to the required value. The phosphate slurry produced in unit 6 enters phosphate separation filter 8. The filtrate from the filter 8, mainly in the form of a solution of calcium chloride, magnesium chloride or other impurities, is collected and removed from the plant in the form of liquid waste, while the solid residue of dicalcium phosphate (or another corresponding phosphate) is directed to a phosphate washing assembly 9, where it is washed with water and re-filtered or re-separated according to phases (the contaminated washing liquid is discharged as liquid waste), and then fed to a phosphate drying plant 10, at the outlet of which the finished phosphate is obtained. The gases generated in the hydrochloric acid leaching unit 4 and the neutralization and phosphate precipitation unit 6 are absorbed and purified in corresponding plants (not shown).
When the recipe of the phosphate raw material used is changed, in the module for preparing hydrochloric acid for leaching 3, on the basis of the concentrated off-gas hydrochloric acid, the optimum concentration of off-gas hydrochloric acid for a given raw material is prepared, which is transferred to the leaching module 4 in the required amount proportional to the amount and mass of the raw material, while in the device for preparing solution for neutralization 7, the solution for neutralization is prepared in the required concentration and amount, thereby providing the optimum conditions and mode for phosphate production.
The solid waste generated in the device 5 for separating the solid and liquid phases after leaching is discarded. The liquid waste from the phosphate separation filter 8 and the washing module 9 is dumped into the sea or, if this is not possible, recycled by known methods, for example by evaporation, into solid waste or commercial products.
The potassium sulfate produced in furnace 8 is sold as a valuable fertilizer alone or as part of a mixed or compounded fertilizer.
The units, devices and components of the apparatus are implemented in a known manner. For example, the hydrochloric acid leaching assembly 4 and the liquid phase neutralization and phosphate precipitation assembly 6 can be made as one or more reactors arranged in series (hereinafter "reactor" is a tank with stirrer, with nozzles for liquid phase input and slurry output, nozzles or ports (with trays and transfer piping) for feeding heat-dispersed phosphate feedstock or solution for neutralization), which can be combined to form a cascade or bank, and combined by co-current with the supply of feedstock or corresponding solution for neutralization to the first reactor or reactors of the cascade (bank) of assemblies 4 or 6. The modules 4,6 can be made on the basis of a multi-zone reactor (extraction unit). In this condition, the basic condition for continuous operation of the plant is that the accumulation reactor, i.e. the tank with or without agitator, is present in the assembly 4,6, where the leaching slurry or phosphate slurry preparation is collected and homogenized between the device 5 and the filter 8, respectively, before distribution. As a build-up reactor, the last reactor of the cascade or the last zone of a multi-zone reactor can be used. In case the phosphate feedstock or the solution for neutralization is fed to a plurality of reactors (determination), the assemblies 4,6 may each comprise means for distributing the phosphate feedstock or the solution for neutralization between the reactors, respectively, which may for example be made in the form of tanks (reactors) with one inlet and a plurality of outlets connected to the reactors by means of pipelines, as well as control and measuring means.
The apparatus 7 for preparing a solution for neutralization can be made in the form of a mixer (reactor with stirrer) where the set values of solid neutralizing agent and water are dosed.
The assembly 3 for preparing hydrochloric acid for leaching can be made in the form of a plurality of accumulation tanks, tanks with mixers (reactors), equipped with pumping, control and measuring devices connected by pipes.
The device 5 for separating the solid and liquid phases after leaching can be made in the form of a typical separation apparatus (separator, filtration device), for example in the form of a filter press.
The phosphate separation filter 8 is also conventionally made in the form of different types of filtering equipment, for example in the form of filter presses, some of which comprise washing assemblies (rotary and belt filters). For example, when a belt filter is used as the filter 8, the phosphate is washed by water supplied onto a part of the belt filter. For filtering and washing the phosphate, a drum vacuum filter or the like may be used.
The phosphate washing assembly 9 and the phosphate drying apparatus 10 are also implemented in a known manner. For example, a tank with an agitator and a settler may be used as a separate scrubbing assembly. In addition, there are fluidized bed dryers, drum dryers, tunnel dryers and other washing and drying devices conventionally used for the production of precipitates.
As the furnace 1, a muffle furnace having an exhaust gas combustion heating and other types of furnaces can be used. The plant 2 for producing hydrochloric acid from off-gases can be implemented in the form of an adiabatic gas cooler, for example an absorber in the form of a series of absorption towers connected to one another in succession, for example an off-gas hydrochloric acid collector-accumulator.
For pumping and dosing liquids and dispersing liquids and slurries, the apparatus uses typical control, metering and pumping equipment, and for feeding solid raw materials, removing products and waste, it may use conveying pipes, pneumatic pipes and other types of equipment.
In view of the above, the device according to the invention can be made and used on an industrial scale.
The present invention will be explained in more detail in the following examples, which, however, should not be construed as limiting the scope of the claims.
Example (b):
example 1
Dry potassium chloride was fed at a rate of 51kg/h into the furnace 1 with heated ceiling of unit A for the production of hydrochloric acid and sulfuric acid having a concentration of 98% was dosed at a rate of 35kg/h into the reaction zone. The process was run at a temperature of 400 c, where potassium sulphate was produced at a rate of 62kg/h without a chlorine potash fertilizer. The hydrogen chloride released in gaseous form was transferred for water absorption, wherein 31% hydrochloric acid was produced in three consecutive absorption columns at a rate of 78 kg/h. Upon dilution with water to a concentration of 12%, hydrochloric acid was transferred at a rate of 200kg/h to unit B for the production of phosphate from phosphate raw material.
A phosphate feedstock in the form of a crushed phosphate having a 1-2mm portion is fed to a reactor cascade of hydrochloric acid leach modules 4 having a stirrer. The crushed phosphate was fed at a rate of 44kg/h to the first reactor of the reactor cascade for ore decomposition. In the same manner, 12% hydrochloric acid was fed at a rate of 200 kg/h. The process was run at a temperature of 60 ℃ and atmospheric pressure. A slurry containing 4.9% phosphate and 4.2% insoluble residue, calculated as phosphorus pentoxide, was fed from the system to the filtration step. During the filtration, the insoluble residue is separated off and the phosphate solution is fed to a neutralization and phosphate precipitation module 6, which is a reactor cascade with a stirrer. The reaction mass was partially neutralized as a result of introducing a 33% aqueous slurry of calcium carbonate at a rate of 30kg/h into the cascade reactor from the apparatus for preparing a solution for neutralization 7 at a temperature of 60 ℃ and atmospheric pressure. At the same time, the pH level in the reaction zone was raised to 3.5, resulting in the conversion of the phosphate to a water insoluble form. The slurry containing 4.1% phosphate calculated as phosphorus pentoxide was transferred from the reactor to a filtration step, where the solid phosphate was separated and transferred to a water washing step in the form of a wet cake at a rate of 26kg/h calculated as dry material until the chloride ion content did not exceed 0.1%, and subsequently to a drying step to obtain a water content of 5%. The 18% calcium chloride solution separated during the filtration process was discarded by transfer.
Claims (6)
1. An apparatus for the co-production of calcium phosphate salts and potassium sulfate comprising:
-a unit for producing phosphate from a phosphate feedstock, comprising a hydrochloric acid leaching assembly having inlets for phosphate feedstock and hydrochloric acid; means for separating the solid and liquid phases after leaching, the inlet of which is connected to the outlet of the hydrochloric acid leaching module and the outlet for the solid phase of which is the outlet of the apparatus for solid waste; a liquid phase neutralization and phosphate precipitation module, the inlet of which is connected to the liquid phase outlet of the apparatus for separating solid and liquid phases after leaching; a device for preparing a solution for neutralization, the outlet of which is connected to the inlet of the solution for neutralization of the liquid phase neutralization and phosphate precipitation module; a phosphate separation filter, the inlet of which is connected to the outlet of the liquid phase neutralisation and phosphate precipitation module and the outlet of which for filtrate is the outlet of the apparatus for liquid waste; a phosphate wash module having an inlet connected to the outlet for phosphate of the phosphate separation filter; a phosphate drying apparatus, the inlet of which is connected to the outlet of the phosphate washing assembly and the outlet of which is the outlet of the apparatus for a commercially available product; and
-a unit for the production of potassium sulphate and hydrochloric acid from potassium chloride and sulphuric acid, comprising a furnace for the production of potassium sulphate with an inlet for potassium chloride and sulphuric acid and an outlet for the product; a plant for producing hydrochloric acid from an off-gas, the inlet of which is connected to the outlet for gas of the furnace; a module for preparing hydrochloric acid for leaching intended to dilute hydrochloric acid to obtain a predetermined concentration, whose inlet is connected to the outlet of the plant for producing hydrochloric acid from off-gases and which has an inlet for water supply and whose outlet is connected to the inlet for hydrochloric acid of the hydrochloric acid leaching module of a unit for producing phosphate;
wherein an optimum off-gas hydrochloric acid concentration for a given feedstock is produced in the module for producing hydrochloric acid for leaching while the solution for neutralization is produced in the apparatus for producing a solution for neutralization at a desired concentration and amount, depending on the formulation of the phosphate feedstock used.
2. Device according to claim 1, characterized in that dicalcium phosphate, tricalcium phosphate and mixtures thereof and mixtures of dicalcium phosphate and/or tricalcium phosphate with phosphate-containing minerals, in particular fluorapatite, are obtained as calcium phosphate salts.
3. The plant according to claim 1, characterized in that concentrated hydrochloric acid is produced in the plant for producing hydrochloric acid from off-gas.
4. The apparatus of claim 3, wherein the hydrochloric acid produced in the apparatus for producing hydrochloric acid from off-gas has a concentration of less than or equal to 33 wt.%.
5. The apparatus of claim 1, wherein greater than 20% of phosphorus pentoxide is used for the production of the calcium phosphate salt.
6. The plant according to claim 1, characterized in that the components for hydrochloric acid leaching and neutralization of the liquid phase and precipitation of phosphate are implemented in the form of one or more reactors arranged in series, which may be combined to form a cascade or a bank, and by co-current combination, wherein the raw material or the corresponding solution for neutralization is supplied to the first reactor or reactors of the cascade or bank.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2016112592 | 2016-04-04 | ||
| RU2016112592A RU2616061C1 (en) | 2016-04-04 | 2016-04-04 | Installation for combined obtaining of phosphate salts and potassium sulphate |
| PCT/RU2017/000191 WO2017176164A1 (en) | 2016-04-04 | 2017-03-31 | Plant for the combined production of phosphate salts and potassium sulphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108602673A CN108602673A (en) | 2018-09-28 |
| CN108602673B true CN108602673B (en) | 2022-12-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201780009438.8A Active CN108602673B (en) | 2016-04-04 | 2017-03-31 | Device for the joint production of phosphate and potassium sulphate |
Country Status (4)
| Country | Link |
|---|---|
| CN (1) | CN108602673B (en) |
| EA (1) | EA030179B1 (en) |
| RU (1) | RU2616061C1 (en) |
| WO (1) | WO2017176164A1 (en) |
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| CN111232940B (en) * | 2020-03-12 | 2023-05-02 | 连云港树人科创食品添加剂有限公司 | Preparation method of tricalcium phosphate and potassium chloride in co-production |
Citations (5)
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|---|---|---|---|---|
| US4435370A (en) * | 1981-09-29 | 1984-03-06 | Pennzoil Company | Preparation of monocalcium phosphate and/or phosphoric acid from phosphate rock |
| CN1152549A (en) * | 1996-11-21 | 1997-06-25 | 戴文清 | Technology for preparing potassium sulfate by two-stage method |
| CN1962421A (en) * | 2006-11-19 | 2007-05-16 | 武善东 | Phosphorite acidolysis method |
| CN101337657A (en) * | 2008-08-06 | 2009-01-07 | 黄明科 | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer |
| CN102417169A (en) * | 2011-08-15 | 2012-04-18 | 武善东 | Acidolysis method of magnesium-containing phosphate rock |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2706145A (en) * | 1950-02-28 | 1955-04-12 | Curtis W Cannon | Production of sulphates and hci |
| US3803884A (en) * | 1969-01-09 | 1974-04-16 | Fitzwilton Ltd | Production of fertilizers |
| US3919395A (en) * | 1970-11-18 | 1975-11-11 | United States Gypsum Co | Process for extraction of phosphorus compounds |
| US4045543A (en) * | 1975-11-12 | 1977-08-30 | Pennzoil Company | Production of potassium sulfate and hydrogen chloride |
| US4328196A (en) * | 1980-09-25 | 1982-05-04 | Pennzoil Company | Production of alkali metal products from alkali metal fluosilicate |
| FI107330B (en) * | 1999-12-03 | 2001-07-13 | Kemira Agro Oy | Preparation of two alkali metal salts by a combined ion exchange and crystallization process |
| BE1015840A3 (en) * | 2003-12-24 | 2005-10-04 | Ecophos | Process leading ore phosphate. |
| CN101066771A (en) * | 2007-05-31 | 2007-11-07 | 聊城大学 | Microwave radiation process for producing potassium sulfate |
| EP2435364B1 (en) * | 2009-05-27 | 2015-05-06 | Easymining Sweden AB | Production of ammonium phosphates |
| CN203922756U (en) * | 2014-06-13 | 2014-11-05 | 江苏瑞和化肥有限公司 | A kind of reactive tank exhaust heat-energy recycling system |
-
2016
- 2016-04-04 RU RU2016112592A patent/RU2616061C1/en active
- 2016-12-26 EA EA201692447A patent/EA030179B1/en unknown
-
2017
- 2017-03-31 WO PCT/RU2017/000191 patent/WO2017176164A1/en active Application Filing
- 2017-03-31 CN CN201780009438.8A patent/CN108602673B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4435370A (en) * | 1981-09-29 | 1984-03-06 | Pennzoil Company | Preparation of monocalcium phosphate and/or phosphoric acid from phosphate rock |
| CN1152549A (en) * | 1996-11-21 | 1997-06-25 | 戴文清 | Technology for preparing potassium sulfate by two-stage method |
| CN1962421A (en) * | 2006-11-19 | 2007-05-16 | 武善东 | Phosphorite acidolysis method |
| CN101337657A (en) * | 2008-08-06 | 2009-01-07 | 黄明科 | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer |
| CN102417169A (en) * | 2011-08-15 | 2012-04-18 | 武善东 | Acidolysis method of magnesium-containing phosphate rock |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108602673A (en) | 2018-09-28 |
| WO2017176164A1 (en) | 2017-10-12 |
| EA201692447A1 (en) | 2017-10-31 |
| EA030179B1 (en) | 2018-06-29 |
| RU2616061C1 (en) | 2017-04-12 |
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