Phosphorus Industry 416h5e
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Chemical Process Technology CHE C322
PHOSPHORUS INDUSTRY
PRODUCTS OF PHOSPHORUS INDUSTRY The major source of phosphorus is from commercial deposits of phosphate rocks in the mineral form Fluorapatite [ Ca(PO4)6F2] The products under the phosphorus industry are: 1. Phosphorus 2. Phosphoric acid 3. Ammonium phosphate 4. Calcium phosphate Fertilizers 5. Nitro phosphate 6. Sodium phosphate 7. Organic phosphate
Phosphorus (P4) Types :
Yellow phosphorus
Yellow phosphorus: Mol. Wt- 123.9 MP- 44.1 oC BP- 280oC Density: material) Solid- 1.82 Liquid-1.74 (45oC) Ignites spontaneously, stored under water Disagreeable odour Extremely toxic
Red phosphorus
Brown/black
Red phosphorus 123.9 593oC More dense (polymeric 2.36 gm/cc Formed by heating yellow- P Higher oxidation resistance and stability
Uses of phosphorus : Phosphorus is used to make H3PO4 acid, which is used to make phosphate fertilizers. An alloy of P called phosphor-bronze is made from P, Cu and Sn. This alloy has many applications as it is a stretchable metallic material. Red P is used to make match stick heads. The compound is a sulphide of red P. used to make smoke bombs used in wars. used in fireworks. Since it is poisonous, it is used for preparing chemicals with zinc phosphide that kill domestic pests like rats. It is also used in the manufacture of P- tetra chloride or Ppenta chloride that are used as chlorinating agents in industries.
Method of production Raw material : Low grade crushed phosphate rock, coke as reductant, and sand as flux. Chemical reactions: 1400-1450 C
a) 2Ca3(PO4)2 + 10C + 6SiO2 BPL(Bone coke flux phosphate of lime)
P4 + 6CaSiO3 + 10CO yellow Phosphorus (+∆H = 680 kcal)
250-450 C b) P4 P4 yellow Phosphorus Red Phosphorus
** Red phosphorous, which is used in the manufacture of safety matches, can be converted into white phosphorous by vaporization followed by condensation.
Flow diagram- Phosphorus
Process Description
Phosphate grinding and sintering (at 1200-1250 ˚C)
Phosphate reduction in Electric furnace
BPL is sintered from sand particle size to marble size lumps This step increases charge porosity to facilitate the release of P4 & CO vapors and decreases entrained dust. Nodulized rock with silica, sand and coke is fed to phosphorus furnace (200-300 V, AC-3 Phase ) which heat the charge to 14001450 ˚ C (sufficient to fuse it and initiate the fluxing and reducing reaction, which leads the P4 formation).
Separation and Purification
CO and P4 vapor mixture are fed to electrostatic precipitator where entrained dust are removed when vapor are hot. Next water spray condenser captures most of the liquid yellow phosphorous and separates it from non-condensible CO gas.
Phosphoric Acid Via Phosphorus Combustion
One of the three routes for commercial production of phosphoric acid.
The ‘dry process’ also called ‘combustion process’. The other two processes operate by acidulation of phosphate rock with strong acids, and are referred as ‘wet process’.
Dry Process
It is obtained via combustion of yellow phosphorus in air followed by hydration of phosphorus pentaoxide product with water. 4P + 5 O2 P4 O10 (∆H = -720 kcal) P4 O10 + 6 H2O 4 H3PO4 (∆H = -45 kcal)
Process Description (Dry Process)
Direct of phosphorus vapor with an air stream and then ing the phosphorus pentaoxide produced directly into a hydrater. The unconverted oxide plus phosphoric acid mist in the exit gases from the absorption tower are captured through an elctrostatic precipitator (demister). CO is also vent off from upper section. Purification of furnace acid is done by the addition of sulfuric acid and silica. Impurities are precipitate out with sludge.
Major engineering problem/issues Electric furnace design:
1.
Power is a major cost component of process High voltage with large reaction zone, reduce electrodes used. Fossil-fueled source of heat for rotary kiln combustion to provide the energy of the endo-therm of the reaction.
Control and operation of furnace:
2.
Changes in composition or ratio of blending of raw materials markedly change the yield
Safety in handling phosphorus :
3.
Molten phosphorous is shipped under water and inert gas. Where elemental phosphorus must be used directly as in incendiaries and matches, conversion to less poisonous red allotropic form with improved oxidation resistance is required.
Phosphoric acid (H3PO4) PropertiesMol. Wt-98 MP- 42.4 ˚C BP – Losses water of hydration at 213 ˚C Density – 1.83 gm / cc at 20 ˚C Completely miscible with water
Incompatibilities: Incompatible with powdered metals, strong bases, iron-containing compounds. Method of production – 1 Wet process a) Strong sulphuric acid leaching b) HCl leaching 2. Electric furnace processes
CONSUMTION PATTERN OF H3PO4
By far, largest use of phosphoric acid comes in the production of fertilizers (>75%)
It is added to foods as a preservative, acidifying agent, flavor enhancer, and clarifying agent
It is also used in processes such as the coagulation of rubber latex, electropolishing, soil stabilization, and as a catalyst in the production of propylene and butene polymers, ethylbenzene, and cumene.
Wet process (With H2SO4) Chemical reactions: a)
Ca3 (PO4) 2 +3 H2SO4 +6 H2O 2H3PO4 +3( CaSO4.2H2O) (∆H=-76.4kcal) Gypsum
b)
Side reactions: CaF2 + H2SO4 + 2 H2O 2HF + CaSO4 . 2H2O 6HF + SiO2 H2SiF6 + 2H2O
Raw materials: 1. The high grade of imported ore is necessary to avoid solubilization of mined rock impurities such as aluminum, silicon, iron oxides.
2.
A beneficiation process can be used on low grade ore which involves milling, screening, hydroseparation, classification and flotation.
Other raw material is strong sulfuric acid.
Wet process ( H2SO4)
Wet/IMI process (With HCl) Chemical reaction: a)
Ca3 (PO4)2 + 6 HCl + 6 H2O 2H3PO4 +3 CaCl2
b)
Side reaction: CaF2 +2 HCl
2HF + CaCl2
6HF + SiO2
H2SiF6
+ 2H2O
Raw Materials: 1. 2. 3.
Phosphate rock of high P2O5 content (>30%) is preferred to avoid excessive acid consumption. Hydrogen chloride gas or concentrated aqueous HCl (>30%) as waste or by product acid can be used. Organic C4 and/or C5 alcohol solvents are used to extract H3PO4 from CaCl2 solution.
Wet process ( HCl)
Major Engineering Issue
1.
H2SO4 Leaching Process
Process design
2.
Fineness of grind Undesired semihydrate and anhydrate at high T Control of sulfuric acid
HCl Leaching Process
1.
Solvent recovery
2.
Steel and lined with acid proof brick Air vent PVC coated steel Storage tank rubber lined steel
Material of constructions
Material of construction
3.
Relatively expensive solvent Efficient solvent handling HCl resistance PVC lined rubber lined impervious grafite
Waste disposal
CaCl2 aq effleunt Siliceous rock residue
Process Comparison
The product acid from wet process using HCl is purer than sulfuric acid acidulation process, and in addition this process claimed to recover 98-99 % of the available P2O5 in the rock, as opposed to experience of the most efficient sulfuric acid processes. Trade hydrochloric acid is normally 2-3 times the price of sulfuric acid.
Phosphate Fertilizers 11 February 2012
Synthetic Fertilizers
Plant growth is required a total of nine major nutrients to proceed normally.
Three of these, C,H and O are obtained from air and soil(as water). Another three Ca, Mg and S are present to a sufficient extent in most ordinary soils. And another three N, P and K are present to a small extent but rapidly depleted from the soil with plant removal for harvesting. Nitrogen contributes to early plant development and greening; Phosphorus assists with early growth and seed or fruit development; Potassium is used by plant for the production of cellulose and starches.
For the fertilizer analysis the three principal ingredients are specified in order as follow:
nitrogen as %N, phosphorus as P2O5, and potassium K2O as three number in sequence separated by hyphens. Example: 0-20-20; 3-12-12; 5-20-20.
Formulation of Major Active Constitutes
Major Nutrients Ammonia solutions, Urea, Superphosphates, Mixed fertilizers, bio fertilizers
Fillers and Conditioners Fillers can include sand, gypsum, rock and assist in even distribution of fertilizers. Conditioners are used to improve soil structure. Examples are sand, specially processed wood waste , synthetic polymer (Krylium).
Coated Fertilizer A variety of coatings have been applied to fertilizer particles to control their solubility in soil. Controlling the rate of nutrient release can offer multiple environmental, economic, and yield benefits.
Calcium Phosphates
Finely ground phosphate rock (Ca3(PO4)2) is occasionally added to fertilizer formulations as a diluent or filler. However because phosphate rock has limited water solubility its action as a phosphate nutrient is small and slow. Hence a more soluble form of phosphate (SSP and TSP) are made by the acidulation of phosphate rock. Generally known as Superphosphates. Two distinct grade
Single Superphosphate – Phosphate rock + Sulfuric acid
P2O5 : 16-20 %
Triple Superphosphate – Phosphate rock + Phosphoric acid
P2O5 : 42-50 %
Superphosphate
Raw Materials
Natural or beneficiated phosphate rock Dilute sulfuric acid (62- 70 % H2SO4)
Acidulation
[Ca3 (PO4)2] 3. Ca F2 + 7H2SO4 (aq) → 3CaH4 (PO4)2 .7Ca SO4 + 2HF The product super phosphate contains the inert gypsum component as well as active calcium dihydrogen phosphate.
SiO2 impurity removal
4HF + SiO2 → SiF4 + 2H2O 3SiF4 + 2H2O → 2H2SiF6 + SiO2 H2SiF6 + 2NaCl → Na2SiF6 +2HCl
Process steps
Mixing : Ground phosphate rock + Diluted H2SO4 Aging of superphosphate in Den Granulation in rotary drum-granulator Drying and Bagging
Triple superphosphate
Much more concentrated than the ordinary superphosphate (45- 46 % of available P2O5).
Triple superphosphate is manufactured by the action of phosphoric acid on phosphate rock.
CaF2. 3Ca3 (PO4)2 + 14H3PO4 → 10Ca (H2PO4)2 + 2HF ↑ (Phosphate Rock)
Process : Very similar to SSP.
(Triple Superphosphate)
Engineering Problem •Sources of particulate emissions : reactor, granulator, dryer, screens, cooler, mills, transfer conveyors. Fluorine compounds and dust particles: Silicon tetrafluoride (SiF4) and hydrogen fluoride (HF) a evolve from the reactors, den, granulator, and dryer. •Bag houses : to control the fine rock particles generated by the rock grinding and handling •Cyclonic scrubbers: scrubbing the effluent gas emissions from the reactor, den, and granulator •Gaseous SiF4 in the presence of moisture reacts to form gelatinous silica, which has the tendency to plug scrubber packings. • use of conventional packed countercurrent scrubbers • other ing devices with small gas ages for emissions control is not feasible. •Scrubber types that can be used are: (1) spray tower, (2) cyclone, (3) venturi, (4) impingement, (5) jet ejector, and (6) spray-crossflow packed.
Ammonium Phosphate Two types of Ammonium phosphate
Mono-ammonium phosphate
Reaction Involve
Reacting ammonia with phosphoric acid, centrifuging and drying in a rotary dryer. NH3 + H3PO4 → NH4H2PO4
Ammonia to phosphoric acid ratio is 0.6 in the preneutralizer and then 1.0 in the granulator
Di-ammonium phosphate. Reaction Involve A two-stage reactor system in order to prevent loss of ammonia. NH3 + H3PO4 → NH4H2PO4 NH3 + NH4H2PO4 → (NH4)2HPO4
The ratios are 1.4 and 1.0 in the pre-neutralizer and granulator respectively
Process description
Neutralization
Granulation
Phosphoric acid and sulfuric acid, added to 3 continuous mixed reactors. Anhydrous ammonia is added in first neutralizer Slurry from third neutralizer is mixed with KCl and feed to rotating drum granulator Rotary adiabatic drier removes the moisture < 1%
Screening
Dried product is separated into three fractions.
Major engineering problem
NH3 Losses
Unreacted and excess NH3 vapor is collected from top of each tank and recharge below the liquid level.
Corrosion
Use type 316 (stainless steel) for hot acid and fume ducts; carbon steel for granulation , drying and screening.
Nitrophosphates
Mixtures of ammonium nitrate and various phosphates made by acidulation of phosphate rock with HNO3 and/or H2SO4
Chemical Reactions:
Nitric Acid Digestion- Ammonia Neutralization Ca3(PO4)2 +6HNO3+4NH3 → Ca(NO3)2+2CaHPO4+4NH4NO3
Nitric Acid-Sulfuric acid Digestion- Ammonia Neutralization
Ca3(PO4)2 +6HNO3+6NH3 + H2SO4 → 2CaHPO4 + 6NH4NO3 +CaSO4
Conversion to monocalcium phosphate 2CaHPO4 + H2SO4 → Ca(H2PO4 )2 + CaSO4
Carbonitric Process
Ca3 (PO4)2 +6HNO3+6NH3 + CO2+ H2O → 2CaHPO4+ 6NH4NO3+ CaCO3
Process description
Pulverized phosphate rock is digested with nitric (or mixed acid)
Digested slurry is pumped to an ammoniating tank
Similar to wet process (Phosphoric acid) Acid strength 25-40 % HNO3
Here chemical reaction completes
Granulation and drying
In rotary equipments Followed by screening in classifying circuit
Major Engineering Problems
Removal of Calcium nitrate
Ca(NO3) is highly hygroscopic (product to lump)
For HNO3 (reaction 1) : digested liquor must be chilled to remove calcium nitrate crystals Mixed acid process (reaction 2)or carbonitric process (reaction 3) : conversion to CaSO4 or CaCO3
Corrosion
Corrosion of digestion and neutralization equipment by HNO3 : 18-8 stainless steel.
SODIUM PHOSPHATE
Numerous combinations of Na with P and O exist, e.g. Sodium Meta, Poly, Ortho, Pyro Phosphate. Ortho- and polyphosphate are made from varying ratio of carbonate, sodium hydroxides and orthophosphoric acid. The principal use of alkali phosphates is in detergent formulation. Other applications include metal cleaning, boiler water treatment, in foodstuffs.
Sodium tripolyphosphate, STPP, Na5P3O10, is the main phosphate present in detergents.
Sodium Tripolyphosphate (STTP)
Overall reaction
5 Na2CO3 + 6 H3PO4 → 2Na5P3O10 + 9 H2O + 5CO2
It is prepared from phosphoric acid by neutralisation with soda ash (sodium oxide) forming sodium hydrogen phosphates.
A powdered mixture of disodium hydrogen phosphate, and sodium dihydrogen phosphate is heated to 500°C to 550°C to produce the stable form of STPP
2 Na2HPO4 + NaH2PO4 → Na5P3O10 + 2 H2O
In a single-stage process the orthophosphate solution is converted from a liquid phase in one process step to become marketable STPP in its solid free-flowing form. The single stage process uses a rotary kiln in which granulation, drying, polycondensation and calcination of the ortho -phosphate solution to finished STPP take place in a single step.
Process Flow Sheet
PHOSPHORUS INDUSTRY
PRODUCTS OF PHOSPHORUS INDUSTRY The major source of phosphorus is from commercial deposits of phosphate rocks in the mineral form Fluorapatite [ Ca(PO4)6F2] The products under the phosphorus industry are: 1. Phosphorus 2. Phosphoric acid 3. Ammonium phosphate 4. Calcium phosphate Fertilizers 5. Nitro phosphate 6. Sodium phosphate 7. Organic phosphate
Phosphorus (P4) Types :
Yellow phosphorus
Yellow phosphorus: Mol. Wt- 123.9 MP- 44.1 oC BP- 280oC Density: material) Solid- 1.82 Liquid-1.74 (45oC) Ignites spontaneously, stored under water Disagreeable odour Extremely toxic
Red phosphorus
Brown/black
Red phosphorus 123.9 593oC More dense (polymeric 2.36 gm/cc Formed by heating yellow- P Higher oxidation resistance and stability
Uses of phosphorus : Phosphorus is used to make H3PO4 acid, which is used to make phosphate fertilizers. An alloy of P called phosphor-bronze is made from P, Cu and Sn. This alloy has many applications as it is a stretchable metallic material. Red P is used to make match stick heads. The compound is a sulphide of red P. used to make smoke bombs used in wars. used in fireworks. Since it is poisonous, it is used for preparing chemicals with zinc phosphide that kill domestic pests like rats. It is also used in the manufacture of P- tetra chloride or Ppenta chloride that are used as chlorinating agents in industries.
Method of production Raw material : Low grade crushed phosphate rock, coke as reductant, and sand as flux. Chemical reactions: 1400-1450 C
a) 2Ca3(PO4)2 + 10C + 6SiO2 BPL(Bone coke flux phosphate of lime)
P4 + 6CaSiO3 + 10CO yellow Phosphorus (+∆H = 680 kcal)
250-450 C b) P4 P4 yellow Phosphorus Red Phosphorus
** Red phosphorous, which is used in the manufacture of safety matches, can be converted into white phosphorous by vaporization followed by condensation.
Flow diagram- Phosphorus
Process Description
Phosphate grinding and sintering (at 1200-1250 ˚C)
Phosphate reduction in Electric furnace
BPL is sintered from sand particle size to marble size lumps This step increases charge porosity to facilitate the release of P4 & CO vapors and decreases entrained dust. Nodulized rock with silica, sand and coke is fed to phosphorus furnace (200-300 V, AC-3 Phase ) which heat the charge to 14001450 ˚ C (sufficient to fuse it and initiate the fluxing and reducing reaction, which leads the P4 formation).
Separation and Purification
CO and P4 vapor mixture are fed to electrostatic precipitator where entrained dust are removed when vapor are hot. Next water spray condenser captures most of the liquid yellow phosphorous and separates it from non-condensible CO gas.
Phosphoric Acid Via Phosphorus Combustion
One of the three routes for commercial production of phosphoric acid.
The ‘dry process’ also called ‘combustion process’. The other two processes operate by acidulation of phosphate rock with strong acids, and are referred as ‘wet process’.
Dry Process
It is obtained via combustion of yellow phosphorus in air followed by hydration of phosphorus pentaoxide product with water. 4P + 5 O2 P4 O10 (∆H = -720 kcal) P4 O10 + 6 H2O 4 H3PO4 (∆H = -45 kcal)
Process Description (Dry Process)
Direct of phosphorus vapor with an air stream and then ing the phosphorus pentaoxide produced directly into a hydrater. The unconverted oxide plus phosphoric acid mist in the exit gases from the absorption tower are captured through an elctrostatic precipitator (demister). CO is also vent off from upper section. Purification of furnace acid is done by the addition of sulfuric acid and silica. Impurities are precipitate out with sludge.
Major engineering problem/issues Electric furnace design:
1.
Power is a major cost component of process High voltage with large reaction zone, reduce electrodes used. Fossil-fueled source of heat for rotary kiln combustion to provide the energy of the endo-therm of the reaction.
Control and operation of furnace:
2.
Changes in composition or ratio of blending of raw materials markedly change the yield
Safety in handling phosphorus :
3.
Molten phosphorous is shipped under water and inert gas. Where elemental phosphorus must be used directly as in incendiaries and matches, conversion to less poisonous red allotropic form with improved oxidation resistance is required.
Phosphoric acid (H3PO4) PropertiesMol. Wt-98 MP- 42.4 ˚C BP – Losses water of hydration at 213 ˚C Density – 1.83 gm / cc at 20 ˚C Completely miscible with water
Incompatibilities: Incompatible with powdered metals, strong bases, iron-containing compounds. Method of production – 1 Wet process a) Strong sulphuric acid leaching b) HCl leaching 2. Electric furnace processes
CONSUMTION PATTERN OF H3PO4
By far, largest use of phosphoric acid comes in the production of fertilizers (>75%)
It is added to foods as a preservative, acidifying agent, flavor enhancer, and clarifying agent
It is also used in processes such as the coagulation of rubber latex, electropolishing, soil stabilization, and as a catalyst in the production of propylene and butene polymers, ethylbenzene, and cumene.
Wet process (With H2SO4) Chemical reactions: a)
Ca3 (PO4) 2 +3 H2SO4 +6 H2O 2H3PO4 +3( CaSO4.2H2O) (∆H=-76.4kcal) Gypsum
b)
Side reactions: CaF2 + H2SO4 + 2 H2O 2HF + CaSO4 . 2H2O 6HF + SiO2 H2SiF6 + 2H2O
Raw materials: 1. The high grade of imported ore is necessary to avoid solubilization of mined rock impurities such as aluminum, silicon, iron oxides.
2.
A beneficiation process can be used on low grade ore which involves milling, screening, hydroseparation, classification and flotation.
Other raw material is strong sulfuric acid.
Wet process ( H2SO4)
Wet/IMI process (With HCl) Chemical reaction: a)
Ca3 (PO4)2 + 6 HCl + 6 H2O 2H3PO4 +3 CaCl2
b)
Side reaction: CaF2 +2 HCl
2HF + CaCl2
6HF + SiO2
H2SiF6
+ 2H2O
Raw Materials: 1. 2. 3.
Phosphate rock of high P2O5 content (>30%) is preferred to avoid excessive acid consumption. Hydrogen chloride gas or concentrated aqueous HCl (>30%) as waste or by product acid can be used. Organic C4 and/or C5 alcohol solvents are used to extract H3PO4 from CaCl2 solution.
Wet process ( HCl)
Major Engineering Issue
1.
H2SO4 Leaching Process
Process design
2.
Fineness of grind Undesired semihydrate and anhydrate at high T Control of sulfuric acid
HCl Leaching Process
1.
Solvent recovery
2.
Steel and lined with acid proof brick Air vent PVC coated steel Storage tank rubber lined steel
Material of constructions
Material of construction
3.
Relatively expensive solvent Efficient solvent handling HCl resistance PVC lined rubber lined impervious grafite
Waste disposal
CaCl2 aq effleunt Siliceous rock residue
Process Comparison
The product acid from wet process using HCl is purer than sulfuric acid acidulation process, and in addition this process claimed to recover 98-99 % of the available P2O5 in the rock, as opposed to experience of the most efficient sulfuric acid processes. Trade hydrochloric acid is normally 2-3 times the price of sulfuric acid.
Phosphate Fertilizers 11 February 2012
Synthetic Fertilizers
Plant growth is required a total of nine major nutrients to proceed normally.
Three of these, C,H and O are obtained from air and soil(as water). Another three Ca, Mg and S are present to a sufficient extent in most ordinary soils. And another three N, P and K are present to a small extent but rapidly depleted from the soil with plant removal for harvesting. Nitrogen contributes to early plant development and greening; Phosphorus assists with early growth and seed or fruit development; Potassium is used by plant for the production of cellulose and starches.
For the fertilizer analysis the three principal ingredients are specified in order as follow:
nitrogen as %N, phosphorus as P2O5, and potassium K2O as three number in sequence separated by hyphens. Example: 0-20-20; 3-12-12; 5-20-20.
Formulation of Major Active Constitutes
Major Nutrients Ammonia solutions, Urea, Superphosphates, Mixed fertilizers, bio fertilizers
Fillers and Conditioners Fillers can include sand, gypsum, rock and assist in even distribution of fertilizers. Conditioners are used to improve soil structure. Examples are sand, specially processed wood waste , synthetic polymer (Krylium).
Coated Fertilizer A variety of coatings have been applied to fertilizer particles to control their solubility in soil. Controlling the rate of nutrient release can offer multiple environmental, economic, and yield benefits.
Calcium Phosphates
Finely ground phosphate rock (Ca3(PO4)2) is occasionally added to fertilizer formulations as a diluent or filler. However because phosphate rock has limited water solubility its action as a phosphate nutrient is small and slow. Hence a more soluble form of phosphate (SSP and TSP) are made by the acidulation of phosphate rock. Generally known as Superphosphates. Two distinct grade
Single Superphosphate – Phosphate rock + Sulfuric acid
P2O5 : 16-20 %
Triple Superphosphate – Phosphate rock + Phosphoric acid
P2O5 : 42-50 %
Superphosphate
Raw Materials
Natural or beneficiated phosphate rock Dilute sulfuric acid (62- 70 % H2SO4)
Acidulation
[Ca3 (PO4)2] 3. Ca F2 + 7H2SO4 (aq) → 3CaH4 (PO4)2 .7Ca SO4 + 2HF The product super phosphate contains the inert gypsum component as well as active calcium dihydrogen phosphate.
SiO2 impurity removal
4HF + SiO2 → SiF4 + 2H2O 3SiF4 + 2H2O → 2H2SiF6 + SiO2 H2SiF6 + 2NaCl → Na2SiF6 +2HCl
Process steps
Mixing : Ground phosphate rock + Diluted H2SO4 Aging of superphosphate in Den Granulation in rotary drum-granulator Drying and Bagging
Triple superphosphate
Much more concentrated than the ordinary superphosphate (45- 46 % of available P2O5).
Triple superphosphate is manufactured by the action of phosphoric acid on phosphate rock.
CaF2. 3Ca3 (PO4)2 + 14H3PO4 → 10Ca (H2PO4)2 + 2HF ↑ (Phosphate Rock)
Process : Very similar to SSP.
(Triple Superphosphate)
Engineering Problem •Sources of particulate emissions : reactor, granulator, dryer, screens, cooler, mills, transfer conveyors. Fluorine compounds and dust particles: Silicon tetrafluoride (SiF4) and hydrogen fluoride (HF) a evolve from the reactors, den, granulator, and dryer. •Bag houses : to control the fine rock particles generated by the rock grinding and handling •Cyclonic scrubbers: scrubbing the effluent gas emissions from the reactor, den, and granulator •Gaseous SiF4 in the presence of moisture reacts to form gelatinous silica, which has the tendency to plug scrubber packings. • use of conventional packed countercurrent scrubbers • other ing devices with small gas ages for emissions control is not feasible. •Scrubber types that can be used are: (1) spray tower, (2) cyclone, (3) venturi, (4) impingement, (5) jet ejector, and (6) spray-crossflow packed.
Ammonium Phosphate Two types of Ammonium phosphate
Mono-ammonium phosphate
Reaction Involve
Reacting ammonia with phosphoric acid, centrifuging and drying in a rotary dryer. NH3 + H3PO4 → NH4H2PO4
Ammonia to phosphoric acid ratio is 0.6 in the preneutralizer and then 1.0 in the granulator
Di-ammonium phosphate. Reaction Involve A two-stage reactor system in order to prevent loss of ammonia. NH3 + H3PO4 → NH4H2PO4 NH3 + NH4H2PO4 → (NH4)2HPO4
The ratios are 1.4 and 1.0 in the pre-neutralizer and granulator respectively
Process description
Neutralization
Granulation
Phosphoric acid and sulfuric acid, added to 3 continuous mixed reactors. Anhydrous ammonia is added in first neutralizer Slurry from third neutralizer is mixed with KCl and feed to rotating drum granulator Rotary adiabatic drier removes the moisture < 1%
Screening
Dried product is separated into three fractions.
Major engineering problem
NH3 Losses
Unreacted and excess NH3 vapor is collected from top of each tank and recharge below the liquid level.
Corrosion
Use type 316 (stainless steel) for hot acid and fume ducts; carbon steel for granulation , drying and screening.
Nitrophosphates
Mixtures of ammonium nitrate and various phosphates made by acidulation of phosphate rock with HNO3 and/or H2SO4
Chemical Reactions:
Nitric Acid Digestion- Ammonia Neutralization Ca3(PO4)2 +6HNO3+4NH3 → Ca(NO3)2+2CaHPO4+4NH4NO3
Nitric Acid-Sulfuric acid Digestion- Ammonia Neutralization
Ca3(PO4)2 +6HNO3+6NH3 + H2SO4 → 2CaHPO4 + 6NH4NO3 +CaSO4
Conversion to monocalcium phosphate 2CaHPO4 + H2SO4 → Ca(H2PO4 )2 + CaSO4
Carbonitric Process
Ca3 (PO4)2 +6HNO3+6NH3 + CO2+ H2O → 2CaHPO4+ 6NH4NO3+ CaCO3
Process description
Pulverized phosphate rock is digested with nitric (or mixed acid)
Digested slurry is pumped to an ammoniating tank
Similar to wet process (Phosphoric acid) Acid strength 25-40 % HNO3
Here chemical reaction completes
Granulation and drying
In rotary equipments Followed by screening in classifying circuit
Major Engineering Problems
Removal of Calcium nitrate
Ca(NO3) is highly hygroscopic (product to lump)
For HNO3 (reaction 1) : digested liquor must be chilled to remove calcium nitrate crystals Mixed acid process (reaction 2)or carbonitric process (reaction 3) : conversion to CaSO4 or CaCO3
Corrosion
Corrosion of digestion and neutralization equipment by HNO3 : 18-8 stainless steel.
SODIUM PHOSPHATE
Numerous combinations of Na with P and O exist, e.g. Sodium Meta, Poly, Ortho, Pyro Phosphate. Ortho- and polyphosphate are made from varying ratio of carbonate, sodium hydroxides and orthophosphoric acid. The principal use of alkali phosphates is in detergent formulation. Other applications include metal cleaning, boiler water treatment, in foodstuffs.
Sodium tripolyphosphate, STPP, Na5P3O10, is the main phosphate present in detergents.
Sodium Tripolyphosphate (STTP)
Overall reaction
5 Na2CO3 + 6 H3PO4 → 2Na5P3O10 + 9 H2O + 5CO2
It is prepared from phosphoric acid by neutralisation with soda ash (sodium oxide) forming sodium hydrogen phosphates.
A powdered mixture of disodium hydrogen phosphate, and sodium dihydrogen phosphate is heated to 500°C to 550°C to produce the stable form of STPP
2 Na2HPO4 + NaH2PO4 → Na5P3O10 + 2 H2O
In a single-stage process the orthophosphate solution is converted from a liquid phase in one process step to become marketable STPP in its solid free-flowing form. The single stage process uses a rotary kiln in which granulation, drying, polycondensation and calcination of the ortho -phosphate solution to finished STPP take place in a single step.
Process Flow Sheet
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