Descripsi process

Direct Neutralization oe Synthetic Manufacture

Raw materials
Basis : 1000 Kg of Ammonium Sulfate
Ammonia 30% = 800 kg
Sulfur acid (90%) = 900 kg
Sources of raw material
Silfur acid can be obtained by contact process as described in module : 4, Lecture 18
Reaction :
2 NH3 + H2SO4 -> (NH4)2 SO4
Ammonium sulfat made with manufactured ammonia is called synthetic ammonium
sulfat. Both saturators and Crystallizers are employed in the synthetic manufacture of
ammonium sulfat. The heat of reaction of anhydrous ammonia and concentrated sulfur acid
obtained by contact process is very high. Hence water evaporated from the crystallizer must be
returned either by means of a condenser or by addition of water.
Ammonia and sulfur acid are introduced via the slurry recycle line. Wherein they react
and superheat the recycling slurry. The slurry is subsequently flashed in the upper chamber at a
reduced pressure (50 580 mm of Hg) . The exothermic heat of rection is removed by
evaporating water either present in the feed acid or added to the system for temperature control
of the process. The loss of water in this zone supersaturates the slurry which recirculates to the

lower suspension vessel via an internal pipe and comes into contact with small crystals and
nuclei. This induces thermal sypson and or by an external pump. This type of crystallizer is
generally know as krystal or Oslo unit.
During operation the PH control is required to be maintained within close imits ( 3.0 to
3.5) Otherwise, thin crystals result. The excessive acidity promotes an overgrowth of crystals in
the pipelines. A higher pH or a lower acidity leads to interior crystals which are difficult to wash
and store and may cause ammonia losses as well.
In another type of reduced pressure crystallizer with a draft tube battle unit, growing
rystals are brought to the flashing slurry. At this surface, super saturation induces maximum
crystal grwth, and sufficient nuclei are present to minimize the scale formation inside the unit.
Several types of atmospheric pressure units are preferred to a vaccum crystallizer because
of their simplicity and lower capital cost. Ammonia is added via a jet-type mixer or a sparger
tube. In another design, a simple absorption column incorporating a few large slotted bubble
hoods is used. In some other case , a single vessel is employedfor both reaction and
crystallization and the heat of reaction is removed by evaporation water . There are design where
separate vessel for reaction and crystallization are used for easy operation and closer control. An
optimum balance between the cooling air energy and the yield of crystal is obtained when the
crystallization temperature is in the range 63 to 66 C.
In most case , the product is recovered from ammonium sulfate slurry by continuous or
automatic bath type centrifuge. The product is washed with water and very dilute and spin dried
again before drying.

For small output, top-feed filters are used since the product can be separated, washed and dried
in single equipment. Ammonium sulfate liquor is corrosive and watted parts of the equipment are
made of stainless steel or rubber lined mild steel . To improve the shape and size, modifiers are
used, such as trivalent metallic salts. Small amount of phosphoric acid or arsenic compounds are
added as corrosion inhibitors.
Sumber : Dr. N .K Patel. Ammonium Sulfate . Natubhai V. Patel College of Pure & Applied
Sciences B.Sc. Semester V Industrial chemistry (Vocational) US05CICV02: Heavy and Fine
Inorganic chemicals .modul 9 lecture 40.
kamis, 7 april 2016 pukul 12.59 pm

Ammonium Sulfate Can Be Synthesized Directly or Produced as a Byproduct

Ammonium sulfate was one of the first popular fertilizers, primarily because it was
produced as a byproduct of coke ovens as early as 1893. While it is still widely used, it has been
supplanted somewhat by urea and other fertilizers that promote green growth in plants. It is still
often used as a component in many fertilizer blends. Ammonium sulfate can be produced as a
byproduct of caprolactam (see Section 4, The BTX Chain), as a coke oven byproduct, or by
direct synthesis. A typical flow diagram for the synthetic process is shown in Figure 5-6.
In this process, anhydrous ammoia and sulfur acid are combined in a pipe reactor. A
highly axothermic reaction occurs, producing ammonium sulfate and a bisulfate solution.

Ammonium sulfate crystals are formed by circulating the solution through an evaporator
where it thickens. A centrifuge separates the crystals from the mother liquor. The crystals contain
1 percent to 2.5 percent moisture, and are dried in a fluidized bed or rotary drum dryer.Dryer
exhaust gases are sent to a particulate collection system (e.g., wet scrubber) to control emissions
and recover residual product. Coarse and fine granules are separated by screening before they are
stored or shipped (Process Description: EPA 1997d, Orica 1999).
Several factors contribute to trouble free storage of ammonium sulfate and other
fertilizers. First, the product should be of uniform crystal size and should contain a low
percentage of lines. It should be dry and preferably have below 0.1% free moisture. No free
acidity should be cooled with dry air under controlled condition after drying, particularly when
the ambient temperature and humidity are sufficient high to cause subsequent moisture
condensation after cooling in a bulk storage pile or in sealed bags. Ammonium sulfate is
commonly shipped in polyethylene or paper bags.

The majority of its production is coming from coking of coal as a byproduct. Ammonium
sulphate is produced by the direct reaction of concentrated sulphuric acid and gaseous ammonia
and proceeds according to the following steps.
1. Reaction of Ammonia and Sulphuric Acid:
Liquid ammonia is evaporated in an evaporator using 16 bar steam and preheated using low
pressure steam. The stiochiometric quantities of preheated gaseous ammonia and concentrated
sulphuric
acid (98.5% wt/wt) are introduced to the evaporator crystalliser (operating under vacuum).
These quantities are maintained by a flow recorder controller and properly mixed by a circulating
pump (from upper part of the crystalliser to the evaporator)
2. Crystallization
The reaction takes place in the crystallizer where the generated heat of reaction causes
evaporation of water making the solution supersaturated. The supersaturated solution settles
down to the bottom of crystalliser where it is pumped to vacuum metallic filter where the A. S
crystals are separated, while the mother liquor is recycled to the crystalliser.
3. Drying of the wet Ammonium Sulphate Crystals
The wet A.S crystals are conveyed (by belt conveyors) to the rotary dryer to be dried against hot
air (steam heated) and then conveyed to the storage area where it naturally cooled and bagged.
The following presents the process block diagram for ammonium sulphate production.

Ammonium sulphate containing 21% nitrogen is another important nitrogenous

fertilizer. It can be obtained as a by-product or may be manufactured synthetically.
Ammonium sulphate is obtained as a by-product; in the steel industry in which ammonia
(another by-product)-from coke ovens is absorbed in sulphuric acid.
Ammonium sulphate is also manufactured by reacting synthetic ammonia with
sulphuric acid. Waste streams from various chemical and metallurgical industries are other
sources of ammonium sulphate e.g. ammonia leaching of ores, production of pigments and
synthetic fibres, manufacture of caprolactam etc produce by product; solutions containing
ammonium sulphate.

Flue gases are another source of the ammonium sulphate. The metallurgical smelters and
coal burning power plants liberate large quantities of SO2 that pollute the atmosphere. The
sulphur dioxide is collected and converted into sulphuric acid, Ammonium sulphate is then
produced by passing ammonia gas through 60% sulphuric acid placed in lead lines vats at about
60C the crystals of ammonium sulphate separate out on cooling.
2NH4OH + H2SO4 (NH4)2SO4 + 2H2O
-

Manufacture

From by-product
Manufacture of by-product ammonium sulphate may be carried out by passing cleaned
coke even gases into an absorption column, counter current to a re-circulating stream of
saturated solution of ammonium sulphate. A 96-98% sulphuric acid is now introduced into the
stream at another point. The neutralisation takes place and the effluent solution containing
ammonium sulphate is passed to a crystalliser, where crystals of ammonium sulphate separate
out on cooling. The crystals are separated either by filtering or by centrifuging and then dried.
The mother liquor overflowing from the crystalliser is acidified and recycled to the absorber.
In an old saturation process ammonium sulphate is produced by passing coke oven gas
and sulphuric acid into a vat containing a saturated solution of ammonium sulphate and then
setting out the crystal.
Synthetic Manufacture: Ammonium sulphate made with manufactured ammonia is
called synthetic ammonium sulphate. Both saturator's and crystallizers are also employed in
the synthetic manufacture of ammonium sulphate. The heat of reaction of anhydrous ammonia
and concentrated sulphuric acid obtained by contact process is very high. Hence water

evaporated from the crystallizer must be returned either by means of a condenser or by addition
of water.
Sulphuric acid may also be obtained as a by-product from alcohol manufacture, nitrating
process, alkylation in petroleum refining and benzene production. The acid obtained by such
processes is called spent acid and contains a large number of impurities.
Ammonium sulphate is dried throughoutly to prevent caking. Free sulphuric acid is
removed either by washing on a centrifuge or filter or by neutralising with weak ammonia
solution.
Daftar Pustaka :
Dr. N .K Patel. Natubhai V. Patel College of Pure & Applied Sciences B.Sc. Semester V
Industrial chemistry (Vocational) US05CICV02: Heavy and Fine Inorganic chemicals UNIT
1.
kamis, 7 april 2016 pukul 12.59 pm

Manufacture
The principal method for the production of ammonium sulfat has long been by the
reaction of by-product ammonia from coke oven with sulfuric acid. Because of the demand for

ammonium sulfate as fertilizer ingredient, and the limitations in supply from the above sources ,
additional amounts have been increase igly produced by the reaction of synthetic and sulfuric
acid .
From Synthetic ammonia and Sulfur Acid
In the past ten years, increasing amounts of hight-grade ammonium sulfat have been
produced directly from synthetic ammonia and concentrated sulfur acid. The process is
essentially the same as the one described previously , using coal gas as one te raw materials. The
actual process details vary among different manufacturers.
One plant produces a high-grade ammonium sulfate as follow : Anhydrous ammonia is
dissolved in water and pumped as an 18 to 28 per cent solution to a reactor where it meets a
stream of sulfuric acid. The solution of ammonium sulfat (maintained at 3.5 Ph ) that form is
pumped into double-effect crystalliizers. Here the water is evaporated under vaccum leaving a
metastable, supersaturated solution, which readily crystallizer.
The crystals grow in size until they are heavy enough to settle to the bottom of the
crystallizer . A slurry, containing 55 to 60 per cent by volume of crysrals, is discharged into
automatic centrifuges. The crystals, obtained in practically theoretical yield, are packaged in
multiwall paper bags . The mother liquor from the centrifuges is returned to the crystallizer.