Ammoniated phosphate fertilizers

Ammoniated

phosphates are formed from the reaction of phosphoric acid (ortho- or poly-) with ammonia. First major production in the U.S. began in about 1920 (MAP). In about 1954 major production of DAP was initiated. Manufacture of the third member of the group, ammonium polyphosphates (APP), began in earnest in the late 1950s. APP is generally fluid, while MAP and DAP are granular.

Main Raw Materials Inputs for the fertilizers industry vary according to the fertilizer type. Phosphate rock is considered the main raw material for the production of phosphate type fertilizers, while in case of nitrogenous fertilizers, ammonia is considered the main raw material. Ammonia is produced by synthesis of nitrogen and hydrogen. The latter is generated either by steam reforming of natural gas, or electrolysis of water. On the other hand, nitrogen is produced either from air liquification as in KIMA- Aswan, or combustion of natural gas

Large quantities of acids are also used, namely sulphuric acid, nitric acid and phosphoric acid. In all fertilizers plants those acids are produced on-site. Raw sulphur is considered the main raw material for the production of sulphuric acid, whereas phosphoric acid production depends on phosphate rock as raw material. The production of nitric acid is based on the on-site produced ammonia.

These catalysts are usually not considered as inputs, instead they are considered part of the equipments. This is related to nature of the reactors in this industry, which are fixed bed reactors. Hence the catalysts only aid the reaction, without reacting themselves. According to several factors, catalysts loose their activity after long operating hours which defer from a catalyst to another. Consequently, they need to be regenerated, usually on-site except for the very expensive catalysts such as platinum alloy catalyst which is regenerated in the manufacturing company. Solvents, carbon dioxide, ground dolomite as coating materials and limestone are also used in fertilizers industry.

Other Inputs (Water, Fuel and Steam) Large quantities of water are consumed for several purposes involving cooling, process, steam generating, floor washing and cleaning, ..etc. Steam is generated in these plants in huge quantities for heating, reforming, stripping and other purposes. This steam is generated in boilers by fuel combustion. The fuel type differs from one facility to the other, including fuel oil (mazot), gas oil (solar) or natural gas. Fuel oil (mazot) is widely used due to its cheap cost. On burning, it generates on burning air emissions with high concentration of sulphur oxides (SOx). Air is also necessary for some operations such as drying and cooling.

* MOLECULAR WEIGHT * MELTING POINT * DENSITY

: : :

115 DECOMPOSES 1.80 gm\cc

* SOLUBILITY

32 gm\100 cc at 15* c

* MOLECULAR WEIGHT * MELTING POINT * DENSITY * SOLUBILITY

: 132 : DECOMPOSES : 1.62 gm\cc : 131 gm\100 cc at 15* c

HOT WASH WATER VENT GAS

SLURRY TO LAGOON

VENT G

H3PO4 GYPSUM
TRAVELLING PAN FILTER

FUME SCRUBBER HF(l)

WEAK ACID WASH WASHED GYPSUM

TO GYPSUM PLANT

RECYCLE H3PO4

40% H3PO4
93-98% H2SO4 COOLING AIR REACTOR HF(g) CLARIFIER SLURRY SLUDGE
SINGLE EFFECT EVAPORATOR

800C AIR+ DUST ROTARY GRANULATOR AIR 1500C

SIDE REACTION
STEAM
GRINDER

Ca3(PO4)2 + CaF2+H2SO4+2H2O 3H2SO4 +2H2O

2H2HF+CaSO4.2H2O 2O) 3PO4+3(CaSO4.2H

COURSE CHEMICAL GRADE FERTILIZER TO BAGGING & SHIPPING

75% H3PO4

FINES

HOT WASH WATER VENT GAS

SLURRY TO LAGOON

VENT G

H3PO4 GYPSUM
TRAVELLING PAN FILTER

FUME SCRUBBER HF(l)

WEAK ACID WASH WASHED GYPSUM

TO GYPSUM PLANT

RECYCLE H3PO4

40% H3PO4
93-98% H2SO4 COOLING AIR REACTOR HF(g) CLARIFIER SLURRY SLUDGE
SINGLE EFFECT EVAPORATOR

800C AIR+ DUST ROTARY GRANULATOR AIR 1500C

SIDE REACTION
STEAM
GRINDER

Ca3(PO4)2 + CaF2+H2SO4+2H2O 3H2SO4 +2H2O

2H2HF+CaSO4.2H2O 2O) 3PO4+3(CaSO4.2H

COURSE CHEMICAL GRADE FERTILIZER TO BAGGING & SHIPPING

75% H3PO4

FINES

DOUBLE DECK SCREENS

* NH3 + H3PO4 -> NH 4 H 2 H PO

* NH3 + NH4 H2 PO4 -> (NH4)2 H PO4

* NH3 +H2SO4 -> NH 4 H SO4

* NH3 +NH4 HSO4 -> (NH4)2 SO4

MAP (Monoammonium phosphate)

There

is no single commodity grade for MAP. Can vary 10-50-0, 11-51-0, 11-550, and others. Basic process for production involves ammoniation of phosphoric acid H3PO4 + NH3 (NH4)H2PO4 Lower quality, high impurity phosphoric acid can be used in MAP production. Thus, manufacture is favored where PR quality is declining.

DAP (Diammonium phosphate)

Single recognized grade in the world marketplace is 18-46-0. Lower analyses may not be sold as DAP. Basic process for production involves ammoniation of phosphoric acid H3PO4 + 2NH3 (NH4)2HPO4 Requires relatively low impurity phosphoric acid. Higher acid quality requirement is becoming a greater issue as phosphate rock (PR) quality declines, particularly in Florida.

The two principal steps are neutralization and granulation. For neutralization,phosphoric and sulphuric acids are added to three continuous mixed reactors.Anhydrous liquid ammonia is added beneath the slurry level in the first neutralizer in an amount equivalent to 80% neutralization . Further ammonia is added in the 2nd and 3rd tanks to obtain conversion to the diammonium salt if a higher N fertilizer is needed.

The exothermic reaction heats the slurry nearly to the boiling point (130*c). Unreacted and excess NH3 vapour is collected from the top of the each tank and recharged below the liquid level.This cuts NH3 losses to less than 3%.
Slurry from the third neutralizer is mixed with KCL and absorbed in a bed of dry recycle fertilizer moving through a rotating drum granulator. This provides a tumbling action to coat recycle material with a slurry film.

A rotary adiabatic drier reduces the moisture to less than 1%, with a 10 minute contact time with air initially at 150*c . Dried product is separated in to three fractions on a double deck screen . A portion of the product from the deck of the lower screen (-6+12) is sent to bagging operations. The balance, together with pulverized oversize and fines, is returned to the granulator. The weight ratio of recycle to product is 6:1-15:1 depending on the grade produced.

MAP and DAP field comparisons

Characteristics of MAP and DAP

MAP 90-100 DAP 90-100

Water soubility, % of total P Saturated solution pH P, moles/l NH4, moles/l Partial pressure of NH3, mm Hg (0.1 M solution) 75 C 100 C 125 C

3.5 2.9 2.9

8.0 3.8 7.6

----0.05

0.9 5.6 28.8

World MAP and DAP production, 1999-2003

World production, 1000 tons 14 000 12 000 10 000 8 000 6 000 4 000 2 000

DAP

MAP

1999

2000

2001

2002

2003

IFA, 2005

MAP Fertilizersoil reaction

Residual granule & immediate soil interface Present either in original granule or formed:

(Ca,Mg)(NH4)(Fe,Al)(PO4)(F,OH).H2O

P-saturated zone Dissolution of Si, Fe, Al, Mn, Ca, Mg, K Precipitation of
DCPD main crystaline P Amorphous Fe & Al phosphates Struvite:Mg(NH4)PO4.6H2O Taranakites: (NH4)3Al5H6(PO4)8.18H2O

5-10% of total P may remain in these compounds in the granule shell

More soluble that variscite or strengite but less soluble than DCPD below pH of 7 Doesnt form in fluid MAP formulations

DAP fertilizersoil reactions

Residual granule & immediate soil interface 5-10% of total P may Present either in original granule or formed: *remain in these compounds in the granule shell . *More soluble that variscite or strengite but less soluble than DCPD below pH of 7 P-saturated zone Much less dissolution of metals except K Precipitation of
Ca and Mg phosphates including DCPD Mixed CaNH4 and MgNH4 phosphates including struvite Colloidal apatite 3 to 5 times more solubilization of organic matter than with MAP believed to interfere with growth of large crystals & allow increased P mobility

Practical summary

The initially acid reaction zone (pH < 4) of MAP:

Helps prevent initial formation of toxic levels of ammonia Promotes precipitation of potentially favorable metastable reaction products, especially in alkaline soils. Increases potential P transport rate across root cell membranes

Practical summary
The initially alkaline reaction zone (pH > 8) of DAP:
Increases potential for ammonia toxicity to seeds or seedlings; can be managed by limiting rate applied in seed contact Results in precipitation of relatively insoluble apatite but also other potentially favorable metastable reaction products, especially in acid soils Solubilizes organic matter believed to increase movement of P away from the granule site Reduces potential P transport rate across cell membranes

Practical summary
Differences in reaction zone characteristics between MAP and DAP diminish with time usually becoming minor within a month or two. The majority of field comparisons of MAP and DAP in the published technical literature that were conducted using typical farmer practices show only minor yield differences, if any, due to P source effects. Recent development of new P fertilizers and additives is increasing the number of field P source comparisons in todays farming systems.

The involved catalysts in the fertilizers industry are as follows: In ammonia production: COO, MOO3 and ZnO for sulphur removal. NiO for primary and secondary reformers. Iron oxide and chromium for CO high shift conversion and copper oxide and zinc oxide for low shift. NiO catalyst for methanation. Iron promoted catalyst for ammonia synthesis. In nitric acid production: platinum/ rhodium catalyst. In sulphuric acid production: vanadium pentoxide catalyst.

Fertilizers industry is a form of secondary chemical production. It is necessary to understand the inputs and processing techniques in order to identify the pollution sources and abatement measures in this industry.

Fertilizers may be categorized into two groups, natural and synthetic fertilizers. Synthetic fertilizers include different types according to their chemical composition, physical status and solubility in water. According to their chemical composition, fertilizers are categorized into three main groups as follows:

Phosphatic fertilizers containing phosphorous as a base element, which is expressed by P2O5 %. Nitrogen fertilizers containing nitrogen as a base element, which is expressed by N2 %. Potassium fertilizers containing potassium as a base element, which is expressed by K2O %.

In addition to the straight fertilizers containing single nutrient (N or P or K) there are the complex fertilizers containing two or three major plant nutrient N.P.K. Enormous varieties of NPK according to their contents of nutrients are available. Liquid fertilizers are also produced worldwide including hundreds of forms containing one or more nutrients together with trace elements. NPK fertilizers are produced in the Egyptian Fertilizer Development Center Pilot Plant, located in Talkha, in limited quantities according to the clients requests. Also in Delta Company there is a plant that produces urea- ammonium nitrate liquid fertilizer (32 % N).

The liquid fertilizers must be free of solids to avoid clogging the slurry nozzles. Concentrated phosphoric acid is used as the basis for high analysis liquids. When reacted with ammonia, it gives neutral solution which does not crystallize at low temperature. If ammoniated under pressure, ammonium polyphosphate forms. This can be stored and shipped as a solid and dissolved readily when needed. Another liquid fertilizer is anhydrous ammonia, vaporized to a gas and ploughed directly into the soil. A combination of solution/ suspension containing 13 % nitrogen and 43 % P2O5 has been developed, to which custom blenders can add potash and trace elements if needed

PRESENTED BY
FIRST BATCH STUDENTS
ABDUL AJEES.M ABDUL AZIZ.AW ABDUL SATHAR.M AKHLIN.A.P.S ANBARASAN.P ARUL KARTHI.S ARUL PAALTHAI.R ARUMUGAM.R ARUN KUMAR.M ARUN PRAKASH.M