LECTURE 10 PHOSPORUS INDUSTRIES PHOSPHORUS (P) IS A VITAL RESOURCE FOR SUSTAINING WORLD AGRICULTURE. Ch 61 Industrial Chem

EXAM II Feb. 1 Wed.

Graduating Students: Review Paper on any Philippine based Chemical Industry. Focus on any: Chemical Transformations and Material Balance (Cost Analysis) Unit Processes / Unit Operations Energy Requirements & Conservation Waste Management & Environmental Protection Program

Format: Choose any: Powerpoint Presentation (15-20 pages) Wikipedia Article format (2-3 pages) Technical report format (3-4 pages) Due: February 24, Friday to:

PHOSPHORUS - USES  Phosphates are used to make special glass that is an important component of sodium lamps.  Phosphorus is an essential nutrient for plants. It is, therefore, added to fertilizers.  In the laboratory, two radioactive isotopes of phosphorus can be used as radioactive tracers.  Calcium phosphate can be used to make fine china.  The strikers for matchsticks are made from phosphorus. Flares and safety matches are also made from phosphorus.  White phosphorus is used in incendiary bombs, smoke screens (such as smoke bombs) and tracer ammunition.

 Tributylphosphate, a compound of phosphorus, is used to extract uranium. This is called the Purex process.  Phosphorus is an important component of DNA and RNA.  Phosphorus is used in the production of steel.  Sodium tripolyphosphate is used in laundry detergents in some parts of the world. It helps in the cleaning of clothes. However, some countries have banned them as it leads to the killing of fish when leaked into waterways.  Other compounds of phosphorus are used in the manufacture of pesticides, food additives, toothpaste and fertilizers.

PHOSPHATE ROCK Phosphate rock (PR) is a globally accepted but imprecise term describing any naturally occurring geological material that contains one or more phosphate minerals suitable for commercial use. Flourapatite admixed with various proportions of other compounds of Ca, F, Fe, Al, and Si. Flourapatite: CaF 2. 3Ca 3 (PO 4 ) 2, an extremely insoluble compound, Ca 10 F 2 (PO 4 ) 6

PHOSPHATE ROCK PROCESSING ACIDULATION: The process of treating a fertilizer source with an acid. The most common process is treatment of phosphate rock with an acid (or mixture of acids) such as sulfuric, nitric, or phosphoric acid. PRODUCTS: Superphosphates, phosphoric acid, triple superphosphates, monoammonium phosphate,

PHOSPHATE ROCK PROCESSING ELECTRIC FURNACE REDUCTION: Phosphate rock is blended with coke (reducing agent) and silica. Charged with electric current forming gaseous P, later condensed to liquid P. PRODUCTS: P, P 2 O 5

SUPERPHOSPHATES Product of the acidulation process: Ca 3 (PO 4 ) 2 + H 2 SO 4 + 2H 2 O → CaH 4 (PO 4 ) 2 + 2CaSO 4 monocalciumphosphate CaF 2 + H 2 SO 4 + 2H 2 O  CaSO 4 + HF 4HF +SiO 2 → SiF 4 + 2H 2 O 3SiF 4 + 2H 2 O → SiO 2 + 2H 2 SiF 6

MANUFACTURE OF SUPERPHOSPHATE Preparation of phosphate rock Mixing with acid Curing and drying of the slurry Milling and bagging

TRIPLE SUPERPHOSPHATE - A more concentrated fertilizer (in terms of P 2 O 5 content) nearly 3X vs. superphosphate. - PR + 14H 3 PO 4 → 10 Ca(H 2 PO 4 ) 2 + HF

PHOSPHORIC ACID Uses: Fertilizers – 85% Detergent materials Animal feed Food, beverages

PHOSPHORIC ACIDS - MANUFACTURE WET PROCESS: Ca 3 (PO 4 ) 2 + 3H 2 O + 4H 2 O  2H 3 PO 4 + 3CaSO 4

Wet process phosphoric acid normally contains 26 to 30 percent P 2 O 5. In most cases, the acid must be further concentrated to meet phosphate feed material specifications for fertilizer production. Depending on the types of fertilizer to be produced, phosphoric acid is usually concentrated to 40 to 55 percent P 2 O 5 by using 2 or 3 vacuum evaporators.

MANUFACTURE OF PHOSPHORIC ACID THERMAL: Raw materials for the production of phosphoric acid by the thermal process are elemental (yellow) phosphorus, air, and water. Thermal process phosphoric acid manufacture involves 3 major steps: (1) combustion, (2) hydration, and (3) demisting.

PHOSPHORUS ELECTRIC FURNACE REDUCTION: 3Ca 3 (PO 4 ) 2 + 6SiO C → CaSiO 3 + P CO

SODIUM HOSPHATES Various forms: Orthophosphates: MSP NaH 2 PO 4 DSPNa 2 HPO 4 TSP Na 3 HPO 4 Manufactuted from Phosphoric acid and Soda ash / caustic soda.

PYROPHOSPHATE / TRIPOLYPHOSPHATE  Used as water softeners Tripolyphosphate: (STPP) NaH 2 PO 4 + 2Na 2 HPO 4  Na 5 P 3 O H 2 O Pyrophosphate: (TSPP) 2Na 2 HPO 4  Na 4 P 2 O 7 + H 2 O

LECTURE 11 POTASSIUM INDUSTRIES PHOSPHORUS (P) IS A VITAL RESOURCE FOR SUSTAINING WORLD AGRICULTURE. Ch 61 Industrial Chem

POTASSIUM USES: Used in the production of alloys (heat transfer) Manufacture of KO 2 in life support systems Manufacture: Na + KCl  K + NaCl

POTASSIUM CHLORIDE Uses: Fertilizer MANUFACTURE: TRONA PROCESS

POTASSIUM SULFATE USES: Fertilizers Production: Na 2 CO 3. 2Na 2 SO 4 (burkeite) + KCl

POTASSIUM BISULFATE USES: Ceramics Manufacture: K 2 SO 4 + H 2 SO 4  2KHSO 4

POTASSIUM HYDROXIDE Caustic Potash Uses: Production of other K salts (K 2 CO 3, KMnO 4, etc) KCl for liquid fertilizers Pesticides and other chemicals Manufacture: Electrolysis

POTASSIUM CARBONATE Uses: -pottery, soaps, adsorbent for acid gases Manufacture: CO 2 + 2KOH + H 2 O

POTASSIUM PERMANGANATE USES: Laboratory oxidizing agents (an expensive oxidizing agent) Manufacture: Passing CO 2 through a KMnO 3 solution KMnO 3 from MnO 2 + KOH + O 2

Potassium Bromide Uses: photographic emulsions, photoengraving, Sedative, Manufacture: 3Fe + 4Br2  Fe 3 Br 8 Fe 3 Br 8 + 4K 2 CO 3 + 4H 2 O  8KBr + 2Fe(OH) 3 + 4CO 2