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Chapter No 1: Introduction
A] History of Development
Hennig Brandt (1630-1710) an Alchemist in Hamburg, Germany discovered
Phosphorous in 1969. Phosphorous burns in air and exist in nature as phosphate.
Carl Wilbelm Scheel(1742-1786) and Johan Gottlieb Gahn (1745-1818) from Sweden
studied the nature of bone , they dissolved bone ash [Ca3(PO4)2 in the form of
hydroxypatite] in Sulfuric acid (H2SO4) so making phosphoric acid. In late 18th
century M.M. Coignet of Lyan, France improved the peltier process of making ash,
acidifying it with sulfuric acid (H2SO4) to produce phosphoric acid.
Ca3(PO4)2 + 3H2SO4 3CaSO4 + 2H3PO4
ManufacturingoffPhosphoricA
AcidusingRockPhosphateeandSulfuriccAcid
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Formula
H3PO4
Molecular weight
98.04
At normal temperature it is a
Appearance
Physical state
Solid crystalline
42.40C (1080F)
. Boiling point
2600C
Vapour pressure
0.0285 mm Hg at 200C
Density at 15.50C
Viscosity at 200C
20 centistokes (80%)
28 centistokes (85%)
140 centistokes (100%)
1.710 at 600F
10
Specific gravity
11
Odour
12
Solubility
13
Refractive index
n20 /D 1.433
14
15
Inodorous at ordinary
temperature
Phosphoric acid is quite corrosive in nature. Its corrosive nature increases with
increase temperature.
16
Vapour density
3.4(Air = 1)
17
Flash point
Not flammable
18
Not applicable
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
2. Chemical Properties :
1. Molten Phosphoric acid slowly undergoes auto dehydration
Auto dehydration of phosphoric acid
2H3PO4 H4P2O7 + H2O
2. Acidic Properties:
a) It is medium strong tribasic acid and this forms three series of salts
i) Primary Phosphates (M1H2PO4)
ii) Secondary Phosphates (M2HPO4)
iii)Tertiary Phosphate (M3PO4)
b) Dissociation of Phosphoric acid
H3PO4
c)
H2PO4-
HPO4-2
PO4-3
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
3. Basic Properties:
a. Molten anhydrous phosphoric acid is a good conductor of electricity,
because of self ionization and formation of phosphotacidium ion P(OH)4+
2H3PO4 H4PO4+ + H2PO4b. Due to slow auto dehydration of phosphoric acid in melts causes reaction
such as
2H3PO4 H4P2O7 + H2O
H4P2O7 + H2O H3O+ + H3P2O7-1
H3P2O7- + H3PO4 H2P2O7-2 + H4PO4Hence molten phosphoric acid has high content of ions.
4. Redox properties:
a) Phosphoric acid in aqueous solution is very poor oxidizing agents
b) Phosphoric acid is good reducing agent
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
3. Beverage Industry :
Phosphoric acid is added to soft drinks as an acidifying agent which imparts
desired tangy taste acid sourness to soft drinks. The pH value is maintained
between 2-4. It is chiefly used in core type beverages but has also found
application in preparation of phosphate beverages such as orange, lemon and
cherry phosphates. The acidity furnished in the form of ortho phosphoric acid is
beneficial to health.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
4. Textile industry :
Here the sults of phosphoric acid such as trisodium phosphates, disodium
phosphates and sodium metaphosphates are generally used for performing the
following purposes:
a. Removal of grease and oil from cotton and wool
b. Dyeing
c. Degumming of silk [Removal of sericin & silk glue]
d. Weighing of silk [Increasing the weight of silk fiber]
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
c. Alkylation :
Alkylation is the reaction of dissimilar hydrocarbons. It is favoured by
high pressure but can be carried out at reasonably low temperature with the
help of the phosphoric acid and catalyst.
7. Photography: Free phosphoric acid is employed in the aniline process for:
a. Reproduction of line subjects
b. To regulate the acidity or alkalinity of the developer both.
c.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
13. Glasses:
Phosphoric acid is used for making glasses with some modified properties as
follows:
a. Optical glasses having desired refractive index dispersion ratio.
b. Glasses having high ultraviolet transmissions
c. Fluorescent glasses
d. Heat absorbing glasses
e. Hydro fluoric acid resistance glasses
MISCELLANEOUS USES
Phosphoric acid is used:
1. As a leavening agent
2. In the preparation of albumin derivatives
3. In the preparation of animal feed supplements
4. As a buffer agent for e.g buffer for high performance liquid
chromatography
5. As the electrolyte in phosphoric acid fuel cell
6. As a pH adjusters in cosmetics and skin care product
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
D] Economic Aspects
1. Demand-Supply position:
Phosphoric acid has many applications as fertilizer & non-fertilizer products.
Therefore the demand for phosphoric acid is a derived demand & the rate of growth in
demand is largely dependent on the rate of growth in the sectors that use it as an input.
The total global consumption of phosphoric acid increases from 37.1 Million Metric
Ton in 2005/06 to 43.7 MMT in 2014/15. The table below shows the increase in
phosphoric acid consumption [P2O5 basic] from 2005 to 2014 on calendar year basis.
Table (1) World Fertilizer Consumption
Year
% Growth in Consumption
(MMT)
2005
37.1
2006
39.0
+5.1%
2007
40.5
+3.8%
2008
41.8
+3.3%
2009
37.6
-5.4%
2010
40.6
+6.3%
2011
39.8
-3.3%
2012
40.3
-0.9%
2013
41.2
+2.2%
2014
43.7
+2.9%
[P. Heffer, IFA, June, 2005/06/07/08/09/10/11/12/13/14]
The increase in the consumption of phosphoric acid leads to the increase in the
demand of the same world demand of the phosphoric acid thus grow from 34.6 MMT
in year 2006 to 43.6MMT in 2014
These increases in demand of phosphoric acid pressurize the industry to operate at
higher capacity. World phosphoric acid capacity in 2007 decreased to 43.2 MMT, but
rebound to 45 MMT of P2O5 in 2008 due to new projects in China & Morocco which
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
is further increased to 55.5 MMT of P2O5 in2014 because of new plants set-up during
this year in countries like Jordan, Tunisia, Saudi-Arabia & Morocco.
The increasing capacity impacts on the global potential supply of phosphoric acid
which was observed to have a marginal surplus of more than 15% over the year of
2006-2004. Global phosphoric acid supply/demand projections show a stable potential
balance which detailed in the table below.
Table (2) World Phosphoric Acid Potential Supply/Demand Balance (Million
Metric Tonnes, P2O5)
Year
2010
2011
2012
2013
2014
Capacity*
47.8
51.0
52.3
53.8
55.5
Total Supply*
39.6
41.5
43.3
45.3
47.1
Fertilizer Demand*
31.3
32.8
34.2
35.5
36.6
Non-Fertilizer use*
5.5
5.6
5.6
6.0
6.2
Distribution Losses
0.7
0.8
0.8
0.8
0.9
Total Demand*
37.6
39.2
40.6
42.3
43.6
Balance*
2.0
2.3
2.7
3.0
3.4
% of Supply
5%
6%
6%
7%
7%
Increase
[M. prudhomme, IFA, June 2010]
*Definitions of various terms in context with the table:
*Capacity: Here capacity is the effective/ Theoretical capacity, representing the maximum achievable production.
*Supply: Supply is computed from the effective capacity, multiplied by highest operating rate achieved in the
respective year.
*Demand: There are two types of demand
a. Fertilizer Demand
b. Non-Fertilizer Demand
a. Fertilizer Demand: It is the ability or willingness of farmers to buy fertilizer at a given probable consumption in
one calendar year
b. Non-Fertilizer Demand: Consumption as non-fertilizer use, referred to industrial use. Net non fertilizer demand
excludes the use of products that are recovered as a by-product from industrial process and then used as fertilizers.
Total Demand = Fertilizer Demand + Non-fertilizer Demand + Distribution losses
*Potential Balance: It is the difference between supply & total demand.
Potential Balance = Supply Total Demand
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
2009-2010
2010-2011
2011-2012
Qty(Tonnes)
Qty(Tonnes)
Qty(Tonnes)
All countries
2692899
2008376
2324532
Morocco
1273174
860313
1084630
Senegal
332198
212676
392742
USA
222308
235231
323771
Tunisia
298101
227292
98371
South Africa
332770
353897
208469
Israel
142757
31322
66330
Saudi Arabia
5620
30381
UAE
13892
China
3998
9173
12074
Lebanon
7682
Indonesia
46929
Malaysia
549
34632
Ghana
14957
Other Countries
81973
77923
41627
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
The export of phosphoric acid decreases drastically to 11798 tonnes in 2010-11 from
143195tonnes in 2009-2010 which is further increased to 18674 tonnes in 2011-12.
2009-2010 Qty
2010-2011 Qty
2011-2012 Qty
(tonnes)
(tonnes)
(tonnes)
All countries
143195
11798
18674
Bangladesh
46675
5229
13
Indonesia
56221
5405
18411
Saudi Arabia
8392
1001
UAE
23
24
23
Mozambique
18
36
20
Sri Lanka
19
10
Taiwan
21815
16
Oman
12
Kenya
52
Nepal
86
Japan
Nigeria
40
Sudan
Other Countries
10044
117
38
[IMYB, 2009-10, 2010-11, 2011-12]
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
2. Process using H2SO4 is the most & most important and may be classified
according to the hydrates form in which calcium sulfates crystallizes, viz,
anhydrates (CaSO4), hemihydrates (CaSO4. H2SO4) and dihydrates
(CaSO4.2H2O). The hydrate form is controlled mainly by temperature and acid
concentration. Table (1) gives the silent features of contemporary process
technology (using H2SO4) in commercial use.
Table (1) Silent Features of Contemporary Process Technologies for fertilizer
grade Phosphoric Acid (H2SO4 route)
Sr
No
Process
Gypsum
Steps
Quality
cost Rs.
in%
(Crores)
Requirement
per ton P2O5
(KWH)
Dihydrate
29
95-96
125
Not good
Hemihydrate 2
31
98-98.5
110
Excellent
31
98-99
110
Excellent
Hemihydrate 1
25
93-94
100
Reported
-Dihydrates
3.
DihydrateHemihydrate
poor
[Executive summary, 2003]
3. The features listed include P2O5 recovery efficiencies, specific energy
consumption, temperature conditions required to be maintained in reactors & recrystallizer and quality of by-product gypsum from various process.
4. The conventional dihydrate process remains the most predominant because of its
low capital cost, low operating temperatures and flexibility of operation. But the
process suffers from relatively low P2O5 recovery & low strength of acid. Newer
process which claims to overcome these limitations of the dihydrate process are
hemihydrates-dihydrate (double filtration stage) and dihydrate-hemihydrate.
5. HCl acidulation process produces technical grade acid. After acidulation, the acid
has to concentrated & purified before used in detergents or food industries. This
process gives CaCl2 as a by-product which is difficult to dispose. Capital cost and
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
cost of production are higher than those sulfuric acidulation plants though the cost
difference is reducing gradually with improving HCl process.
6. Electro-thermal reduction of phosphate rock produces very pure phosphoric acid,
but the cost of production is extremely high because of high cost of power in India
capital cost is highest for the plant based on this technology.
Manufacturer
No
1
Installed
Process Licensor
Capacity
FACT Limited,
33,000
Conductor
Dorr Oliver, U.S.A.
Udyogmandal
2
Hindustan
Dorr Oliver
10,696
Limited
3
Engineering
52,500
Societe-de-Prayon
Simon Carves
Belgium
Ltd. U. K.
Hitachi Zosan
Japan
Coromandel
91,000
Fertilizers Ltd
5
Dorr Oliver
Ltd, U.S.A.
17,385
Pandit Ltd.
Societe-de-Prayon
Charamsi
Belgium through
Morarji
Chemical Co.
Ltd.
Fact Limited,
1,18,800
Cochin
Societe-de-Prayon
FEDO
Hindustan Zinc
26,800
Not Available
Not Available
Hindustan Lever
41,850
Mac-him/Simchem
FEDO
2,25,000
Hindustan
Ltd.
9
Paradeep
Phosphate Ltd.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Manufacturer
No
Installed
Process Licensor
Capacity
Engineering
Conductor
RCF Ltd.
30,000
Nissan, Japan
PDIL
SPIC Ltd.
52,800
Nissan, Japan
Hitachi zosen
Japan
HFC Ltd.
27,600
PDIL
PDIL
C. Plants Based on Dihydrate-hemihydrate (Central Glass Prayon Process)
Sr
No
1
2
Manufacturer
Hindustan Copper
Ltd
FCI Ltd
Installed
Capacity
68,000
1,19,000
Process Licensor
Societe-de-Prayon
Belgium
Societe-de-Prayon
Belgium
Engineering
Conductor
FEDO
FEDO
Manufacturer
No
1
Installed
Process Licensor
Capacity
Ballarpur Industries
24,000
Engineering
Conductor
Process)
Pvt. Ltd.
Manufacturer
No
1
Installed
Process Licensor
Capacity
Star Chemicals (Bombay)
Engineering
Conductor
6000
TVA, U.S.A.
Pvt. Ltd
2
Excel Industries
NA
TVA, U.S.A.
NA
TVA, U.S.A.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Manufacturer
No
1
Installed
Process Licensor
Capacity
Dorr Oliver, Ltd,
Engineering
Conductor
70,000
Self
34,000
Societe-de-Prayon
NA
U.S.A.
2
Simon Carves
Ltd. , U.K.
Hitachi Zosen,
Belgium
65,000
Japan
4
5
Chemico, U.S.A.
Jacobs
NA
14,000
U.S.A.
U.S.A.
U.S.A.
U.S.A.
Michim/Simchem
NA
International Inc.
B. Plants Based on hemihydrates-Dihydrate Process
Sr.
Manufacturer
No
Installed
Process Licensor
Capacity
Engineering
Conductor
Nissan, Japan
1,10,000
Self
54,000
Nissan, Japan
Nissan, Japan
32,000
Nissan, Japan
Nissan, Japan
Plants
C. Plants Based on Hydrochloric Acid (IMI) process
Sr.
Manufacturer
No
1
Installed
Process Licensor
Capacity
AEA, France
56,000
Engineering
Conductor
Self
Manufacturer
No
1
Installed
Process Licensor
Capacity
TVAs, U.S.A.
NA
Engineering
Conductor
Self
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
7. Research & development has been made during the last 30 years and modification
in the process has been achieved. Some have modified effluent disposal system
and have also developed methods for better utilization of gypsum.
8. FEDO, PDIL, GSFC Ltd, RCF and Ballapur Industries Ltd. Are the companies
who have reported doing some R & D work pertaining to phosphoric acid.
Unfortunately, there has been very little commercial application of in-house R &
D work done in the country.
9. There are many Phosphoric acid producing Industries across the world. Here are
some of those Industries with their capacities mentioned below in Table (3)
10. These Industries across the world had made lots of advancement in the
manufacturing process, purification process of phosphoric acid. They had
discovered the technology for the extraction of fluorine and uranium from the
phosphor-gypsum. Some of these technologies are also being imported to India.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
:Ca10(PO4)6F2
d. Odor
:Odorless
e. Melting Point
:71400C
f. Solubility
:Insoluble
g. Relative Density
:3.2 Kg/lit
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Following are the general specification of rock phosphate recommended for use in
manufacturing of phosphoric acid:
Component
% in Rock phosphate
P2O5
32-34%
CaO
1.5% (max)
Fe2O3 + Al2O3
2.0% (max)
CO2
3.0% (max)
SO3
SiO2
2.5-5% (max)
4% (max)
MgO
0.5% (max)
Cl
0.015% (max)
Organic Matter
1.5% (max)
3. Chemical Properties:
i. Reaction of rock phosphate with sulfuric acid:
Ca10(PO4)6F2 + 10H2SO4 + 20H2O 6H3PO4 + 10(CaSO4.2H2O)
ii. Reaction of rock phosphate with hydrochloric acid:
Ca10(PO4)6F2 + 6HCL + 6H2O 2H3PO4 + 3CaCl2
iii. Reaction of rock phosphate with phosphoric acid
2Ca10(PO4)6F2 + 14H3PO4 10Ca(H2PO4)2 + 2HF
iv. Reaction of rock phosphate with silica gives elemental phosphorous
2Ca3(PO4)2 + 10C + 6SiO2 P4 (Yellow Grade) + 6CaSiO3 + 10CO
4. Components of Rock phosphate:
For production of phosphoric acid main criteria for rock phosphate are:
a. P2O5 content: 33-38% P2O5 rock phosphate is considered as high grade.
For production of phosphoric acid high grade rock phosphate is required.
b. CaO content: It affects the sulfuric acid consumption. Each process of
CaO needs an equivalent of 17.5 Kg sulfuric acid per ton of rock
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
5. Manufacturing Processes:
The phosphate rock having maximum P2O5 content & a minimum of impurities is
suitable for the production of phosphoric acid. However rock phosphate contains
different types of impurities & non-phosphate materials. It is important to remove or
minimize all the contents of these impurities in rock phosphate.
The separation of phosphate rock from impurities & non-phosphate materials for use
in manufacturing of phosphoric acid consist of beneficiation, Drying and calcining at
some operation and grinding. Rock phosphate from the mine is first sent to separate
sand & clay and to remove impurities. The wet beneficiated rock phosphate may be
dried or calcined depending on its organic content. Dried or calcined rock is ground in
roll or ball mills to a fine powder.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
In most of the cases to reach commercial grade of some 30% of P2O5, only screening
or drying is required. For sedimentary rock suitable, suitable techniques for economic
ore concentration re-crushing & screening or grinding followed by pneumatic particle
size selection and washing and disliming by hydrocyclones or classifiers.
6. Uses and applications:
a. It is used in production of phosphoric acid as a raw material.
b. It is used in production of fertilizer such as single superphosphate, triple
superphosphates and ammonium phosphate as a raw material.
c. It is used in production of elemental phosphorous as raw material.
d. In some cases it is directly used as a fertilizer.
e. Rock phosphate is used in animal feed supplements, food preservatives,
anticorrosion agent, cosmetics, fungicides, ceramics, water treatment and
metallurgy.
B. Sulfuric Acid:
1. Introduction
Beside rock phosphate sulfuric acid is second raw material needed for phosphoric acid
production. It is preferred to utilize strong phosphoric acid in order to obtain high
P2O5 content or washing efficiency. Sulfuric acid is the first choice for commercial
processes, because it produces insoluble calcium sulphate (Gypsum) which can be
easily filtered. Wet process phosphoric acid is the major world sulfuric acid
consumer, with nearly 50% of the total production.
Sulfuric acid is the highly corrosive strong mineral acid. For wet process phosphoric
acid production generally 72-75% concentrated sulfuric acid is used. This
concentration of sulfuric acid is obtained by mixing strong sulfuric acid(97%
minimum conc.) and weak sulfuric acid(67% min conc.) in the mixing vessel.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
2. Physical Properties:
a. Molecular Formula
: H2SO4
b. Molecular Weight
: 98
c. Appearance
d. Odour
: Odourless
e. pH
: 0.3 (1 N solution)
f. Vapour Pressure
: <0.0012mmHg
g. Vapour Density
: 1.2 Kg/m3
h. Boiling Point
: 290C
i. Melting Point
: 10.33C
: Soluble in water
l. Specific Gravity
:1.841
97% (min.)
Residue on ignition
0.054%
0.01%
0.0003%
<1%
3. Chemical Properties:
a. Reaction of sulfuric acid with water: It is highly exothermic reaction as of
formation of hydronium ions.
H2SO4 + H2O H3O+ + HSO-4
b. Acid-Base reaction: Sulfuric acid reacts with most bases to give
corresponding sulphate. Consider a reaction of sulfuric acid with copper oxide.
CuO + H2SO4 CuSO4 + H2O
Sulfuric acid can also be used to dispose weaker acid from their salts.
Consider reaction of sulfuric acid with sodium acetate.
H2SO4 + CH3COONa NaHSO4 + CH3COOH
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
c. Reaction with metals: Sulfuric acid reacts with metals producing hydrogen
gas and salts. It attracts reactive metals such as iron, aluminum, zinc,
manganese and nickel.
Fe + H2SO4 H2 + FeSO4
d. Reaction with sodium chloride: Sulfuric acid reacts with sodium chloride
and gives hydrogen chloride gas and sodium bisulfate
NaCl + H2SO4 NaHSO4 + HCl
e. Reaction with non-metals: Sulfuric acid oxidizes non-metals such as carbon
& sulfur.
C + 2H2SO4 CO2 + 2SO2 + 2H2O
S + 2H2SO4 3SO2 + 2H2O
f. Electrophilic aromatic substitution: Benzene undergoes electrophilic
aromatic substitution with sulfuric acid to give the corresponding sulfonic
acid.
O
H2SO4,SO3
OH
H2O
O
4. Manufacturing process
a. Contact process or DCDA process: Sulfur is burned to produce sulfur dioxides
S + O2 SO2
This is then oxidized to sulfur trioxides in the presence of vanadium oxide catalyst.
2SO2 + O2 2SO3
The sulfur trioxide is absorbed into 97-98% H2SO4 to form oleum (H2S2O7) also
known as fuming sulfuric acid.
H2SO4 + SO3 H2S2O7
H2S2O7 + H2O 2H2SO4
b. Wet sulfuric acid process: Sulfuric acid is burned to produce sulfur dioxides
S + O2 SO2
This is oxidized to sulfur trioxides using oxygen and vanadium oxide as catalyst.
2SO2 + O2 2SO3
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
F] Justification
1. Syllabus requirement: The manufacturing of phosphoric acid by wet process
using sulfuric acid and rock phosphate as raw material has been previously
studied as part of syllabus in subject Chemical Process-I (6th Semester,
Mumbai University). This study provided information about raw materials,
process detail, flow sheet and engineering problems of manufacturing process.
2. Significance of phosphoric acid: Phosphoric acid serves as an intermediate
product for most of the fertilizers used in India. India is agro based country. It
requires large production of phosphoric acid based fertilizers which are
ammonium phosphate, triple phosphate, and liquid mixed fertilizers.
Phosphoric acid also used in dental science.
3. Uses and application: Phosphoric acid serves large application in fertilizers,
pharmaceutical beverages, textile, oil refinery, sugar, soap and detergents and
glass industry. Phosphoric acid used as catalyst to alter the composition of
hydrocarbons in dehydration, polymerization and alkylation process. It also
used in photography, rust removal, water treatment and fire retardant as main
component.
4. Import and export requirement: Demand of phosphate fertilizers has grown
rapidly in India. India has limited resource of rock phosphate therefore relied
heavily on import of both phosphate rock and phosphoric acid for production
of fertilizers. India is a great importer of phosphoric acid. Out of total trade of
approximately 5 million tons. India imports more than 2.5 million tons per
year because of great demand of fertilizers. India exports phosphoric acid to a
very small extent
5. Storage, Handling, Transportation, Loading and unloading: Phosphoric
acid is non-flammable, non-toxic and less corrosive in nature. Therefore it is
easy to storage, handling and transportation. Storage facilities required for
phosphoric acid are relatively more expensive than that of the solid fertilizer.
Phosphoric acid is transported in rubber lined steel tankers or stainless steel
tankers. The clarified acid is transported over long distance in special ocean
going ships. In India phosphoric acid is imported in such ships.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
6. Special significance in fertilizer industry: Phosphoric acid has find its ample
use in fertilizer industry. It has a special significance in manufacturing of
complex
fertilizers
like
nitrophosphate,
ammonium
nitrophosphate,
superphosphoric acid etc. also its serves a important raw material in the
production of some industrial phosphate like sodium phosphate and calcium
phosphate.
7. Importance of byproduct produced along with phosphoric acid: In
manufacturing of phosphoric acid, important byproduct i.e gypsum and
fluosilicic acid is obtained. This byproduct also has many industrial
importances. Gypsum is soft sulfate mineral, it can be used as main
constituents in many forms plasters, fluosilicic acid is used as fluoridation
agents for drinking water.
By considering all above points it is very much important to study the manufacturing
of phosphoric acid using rock phosphate and sulfuric acid as a raw material in
detailed.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
are cooled with air, which is then used to dry the materials prior to grinding and
agglomerates prior to entering the kiln.
It utilises resources that are unsuitable or difficult to process by wet acid methods.
Improved hard process also has several environmental advantageous. Regardless of
the ore use, process produces solid waste in the form of amorphous agglomerates
suitable for aggregate uses rather than gypsum piles. The improved Hard process is a
dry process so threats to ground or surface water reduced. It also makes use of green
sulphur petroleum coke. Improved hard process phosphoric acid is produced
relatively pure, high concentration acid suitable for use of fertilizers. [Dr. Megy J. A.,
2002]
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
compound having a high volatility, such as arsenic halide and arsenic hydride and the
compound evaporates at treatment temperature. The compound capable of generating
hydrogen halide under the acidic condition is a halide of iron(II), copper(I) or tin(II),
which is used to remove arsenic from the phosphoric acid.
The arsenic content of 10 to 100 ppm of general industrial phosphoric acid can be
reduced to about 1 ppm by treating phosphoric acid with hydrogen halide. The total
cost for treatment is low and since sodium compound is not used, unlike the
conventional method sodium does not remain in large amount in product phosphoric
acid. [Hotta K. & Kubota F., 2005]
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
support result in calcium sulphate accumulation in the opening of the movable filter
support. Which include removing filter from the filter support and causing the filter
support to move in cyclical manner and the filter is removed from the filter support.
During cyclical motion, a plurality of nozzles in the spray bar, may spray pressurized
fluid towards the surface of the filter support. This occurs through multiple cycle
movement such that the spraying results in a sweeping motion across the surface of
the filter support. After a majority of openings in the filter support are substantially
free of calcium sulphate blockage spraying may be terminated.
Fluid is sprayed at a pressure greater than 5000 psi to clean the filter support. Wherein
the fluid is sprayed at a flow rate between 450-900 gallons per minute at an angle
perpendicular to the surface of the filter support, which substantially cleans all the
openings of filter support and makes filter support free of calcium sulphate. [Smith G.
L. & Jackson J. D., 2010]
Other literature shows how continuous melt suspension crystallization process is used
for the purification of phosphoric acid, which consist of a. cascade of mixed product
removal (MSMPR) crystallizer and a gravity wash column for subsequent solid liquid
separation. The crystallization equipment consist of MSMPR crystallizer and a wash
column (length 1200mm). Seed crystals were prepared from a solution of reagent
grade acid (85% H3PO4 & specific gravity of 1.7) & cooled to -5oC to -10oC & size is
maintain to 0.1 mm. After 1 hour of crystallization, magma is entrained to the top of
wash column by screw propeller stirrer.
Because of density difference between crystal and liquid, crystals in the magma
settled down to from a loosely packed bed, which was melted to the bottom of column
having temperature equal to melt temperature of phosphoric acid hemihydrate. Part of
the melt is withdrawn while part of it returned as wash liquid & crystals is enabled.
The melt containing impurities was extracted as residual at the top of column. Thus,
feeding in the crystallizer and withdrawing of the product and the residual at the
bottom & top of the column respectively allows the continuous operations of the
crystallization equipment. Purity of the crude crystals descending in the wash column
increases due to:I.
II.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
III.
IV.
Sweating of the crystals in contact with the hot melt or adiabatic recrystallization of the crystals.
DepartmentofChemicalEngineering,SSJCOE,Dombivli(E),[20142015]Page|35
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
which passes the coolant having temperature ranges from -20 to -15 0C. Thus the
temperature of the acid between -9 and -13 0C is achieved.
The overflow is then passed to the agitated crystallizer comprising of agitator shaft
carrying impeller blades. The residence time within crystallizer should be less than 1
minute. For commercially crystallizer, residence time as short as 10 seconds is
prefered. The acid is again passed through the acid cooler which is operated with
respect to first cooler. Because agitation provides higher heat transfer rates due to
which process becomes thermodynamically unstable and there may be the risk of
increase in unwanted crystallization occurring in the device. It provides a continuous
process, since the seed crystals always present in the crystallization vessel to cause
continued crystallization of seed. Once the process setup it is self- sustaining.
Using this method of seed preparation the process becomes continuous by only 1st
seed supply (extraneous), also the acid of concentration (45 - 50% P2O5) is obtainable
from the process. [Mollera P., et. al, apr 14, 2001]
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Pillai J. K explains how a digested slurry from a wet process phosphoric acid
production process is dewatered by gravity assisted vacuum filtration using as a
filtration aid an aqueous solution of a polymeric filtration and that has been subjected
to high shear mixing to enhance the performance of the filtration aid and enhance the
filtration. The yield of WPA process is encountered both an extreme need for
filtration efficiency and extreme filtration conditions. Filtration aids, particularly
polymeric filtration are often used to enhance the filtration process. Enhancement
generally sought from filtration aids is:i. Increase in filtration rate
ii. Minimization or elimination of solids in the filtrate
iii. Minimization of liquid in the filter cake
In WPA process the product obtained is desired to be in concentrated form,
enhancing the filtration process and reducing the amount of acid associated with the
filter cake are very important. The present invention provides a process for the
dewatering of digested slurry from a wet process phosphoric production digestion
process, in which an aqueous solution of polymeric filtration acid is added to the
digested slurry. The dewatering is accomplished with gravity assisted vacuum
filtration while the temperature of slurry remains in the range from 63 0C 135 0C the
liquid phase contains about 28 to 42 wt % soluble P2O5. [Pillai K. J., et. al., 2003]
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Amin M. I. along with other collegues proposed the solvent Extraction of iron from
Egyptian Wet process phosphoric acid is investigated. This process is important
because of the presence of iron in phosphoric acid results in viscosity & consequently
decreasing the filtration rate. Before iron extraction pretreatment is given to the
phosphoric acid using diethyl-hexyl phosphoric acid. Crude acid is mixed with
bentonite for approx 30mins & left for settle down. Flocculating agents such as
Polycrylamide type is added to enhance the settlement of suspends.
Extraction experiment is carried out in mechanically agitated thermostatic beaker
containing iron in 50 ml phosphoric acid & 100 ml of D2EHPA. This mixture is
agitated at 400 rpm speed. After 5 mins Organic & aqueous phase are separated. Iron
conc. In aqueous phase is determined by adsorption spectrometer. Conc. of iron in
organic phase is calculated by difference of iron in aqueous phase before & after
extraction. Concentrated phosphoric acid (44% P2O5) was purified by solvent
extraction using mixture of butanol & octanol in 3 steps. These trials are expensive
because of applying scrubbing process.
Removal of iron from wet process phosphoric acid is investigated by solvent
extraction using solvent diethyl hexyl phosphoric acid. The % removal of Fe was
69.3- 99.9 % for Egyptian phosphoric acid & diluted phosphoric acid is a obtained
without scrubbing process. These trails are expensive because of applying scrubbing
process so the main goal of this work is extraction of iron from Egyptian wet process
phosphoric acid without applying scrubbing during purification process.[Amin M. I.,
2014]
One of the journal gives us the basic overview of central prayon process for
manufacturing/ production of phosphoric acid by Dihydrate-hemihydrate process.
Overviews of major equipments are given along with process flow diagram. In his
IFA symposium presentation, paul smith reviewed the processes presently available &
examined the features of each process. He observed prayon enjoys considerable
expertise in licensing Dihydrate plants, enjoying market leadership. Prayon pioneered
the use of flash cooler to remove the heat of reaction. The flash cooler was originally
designed in 1950s & has progressively upgraded. Prayon currently offers the 4
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Hydrogen peroxide was used as oxidizing agent to ensure that all Fe(2) & U(4) ions
are oxidized to Fe(3) & U(6). The advantages of hydrogen peroxides are that it forms
no precipitates with other reactants. The clays of iliminite were used to remove humic
acid & suspended materials from crude phosphoric acid. Flocculating agents was
added & the mixture was left for 10 minutes for settling. Extraction process was
carried out by shaking 5ml of organic solvent with 5ml of crude acid in separating
funnel for 15 min at 25C. Maximum removal of organic matter such as Fe, Fluorine
and Uranium is achieved by this process. Extraction of P2O5 can also be done by
using various alcohols. [Awwad N. S., et. al., 2013]
One of the arab journal gives short overview of the phosphoric acid production
process (wet process) and the causes of corrosion in the various equipment of plant.
The corrosion resistant materials to be used for all major equipments of plant are
explained briefly. Corrosion prevention or resistance for
a. Reactor: The first stage for which special material are required is the reactor for
digesting the ore. The reactor vessel is made of cement or carbon steel with nonmetallic linings and sometimes augmented with acid resisting bricks.
b. Mixers: The mixers are made up of stainless steels such as VDMR alloy 904
L(1.4539) or VDMR alloy 926 (1.4529). The application of this alloys are however
limited by the increasing impurity in phosphate ores and higher temperature for
digesting the ore. Material VDMR alloy 31 (1.4962) is particularly resistant to
corrosion in phosphoric acid slurring.
c. Filter: The filtration equipment also requires special materials. In particular good
resistance to pitting and crevice corrosion is a criterion here. The material used for
this plant section are for example 300 series stainless steels VDMR alloy 904
L(1.4539) or VDMR alloy 926 (1.4529). Even the higher resistance for pitting and
crevice corrosion can be achieved with VDMR alloy 31(1.4560).
d. Evaporator and heat exchanger: It is either equipped with metal tubes or is mode of
graphite. It has been shown that metallic heat exchanger operates satisfactorily when
hot water is used as heating medium. The solids settling on the tube walls, mainly
gypsum are easily removed by routine cleaning, which prevents corrosion after
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
deposits. VDMR alloy 28 (1.4563) and VDMR alloy 31 (1.4562) are used for the heat
exchangers.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
A] Di-hydrate Process
Process Description:
The description process comprises four stages: grinding, reaction, filtration and
concentration. For di-hydrate process particle size acceptable is (60%-70% less than
150 m), which are attained either by ball mill or rod mill. The tricalcium phosphate
by reaction with conc. Sulphuric acid is converted into phosphoric acid and insoluble
calcium sulphate. The operating conditions for di-hydrate precipitation are 26%-32%
P2O5 and 70 0C- 80 0C. This temperature is controlled by passing the slurry through, a
flash cooler or by air circulating cooler. Filtration separates the phosphoric acid from
the calcium sulphate di-hydrate. On filtration, the gypsum is given at least two stages
of washing to ensure a satisfactory recovery of soluble P2O5.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Di-hydrate Process
Advantages:
1. Single stage filtration, simple in design.
2. Flexibility of rock phosphate.
3. Ease of operation.
4. Required lower grades of material of construction.
5. Low maintenance cost and high operating factors.
6. Easy transport of gypsum slurry.
Disadvantages:
1. Produces acid at 26%-32% P2O5.
2. Normally requires steam for evaporation.
3. Acid has high level of Al and F.
4. P2O5 efficiency 94%-96%.
5. Requires weak acid storage and evaporation.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
B] Hemihydrate Process
Process description:
The storage is similar to those of the di-hydrate process but grinding may be
unnecessary. Reaction occurs and operating conditions are selected in this process so
that the calcium sulphate is precipitated in the hemihydrates form. It is possible to
produce 40%-52% P2O5 acid directly, with consequent valuable savings in energy
requirements. Hemihydrate crystals tend to small and less well formed thus
hemihydrates slurries tend to be more difficult to filter.
Process block diagram:
Hemihydrate Process
Advantages:
1. Single stage filtration.
2. Produces strong acid directly 40%-48% P2O5.
3. No intermediate storage if acid is produced at user strength.
4. Uses coarse rock.
5. Ease of operation.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Disadvantages:
1. Limited number of rocks process industrially.
2. Large filter area required for 48% P2O5 acid.
3. High lattice loss, low P2O5 efficiency [90%-94%]
4. Produces impure hemihydrates.
5. Tight water balance.
6. Requires higher grade alloys.
7. Care required in designing and shut down.
C] Hemihydrate Di-hydrate Process
Process description:
It is possible to obtain 40%-52% P2O5 acid directly, by acidulating under hemihydrate
conditions and separating hemihydrate before recrystallization, in this process. Thus
the sequence is as follows:
i.
ii.
Separate product.
iii.
iv.
The additional filter and the other equipment required, add to the typical cost of the
plant enable savings to be made on evaporation equipment.
Advantages:
1. It produces strong acid directly [40%-52% P2O5]
2. It produces pure acid (low SO4, Al, F)
3. Limited post precipitation.
4. Uses coarse rock.
5. Low sulphuric acid consumption.
6. High P2O5 efficiency [98.5%]
7. Produces a pure gypsum.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Disadvantages:
1. Two stage filtration, lower utilization.
2. Limited number of rock processed industrially.
3. Care required in design and shut down.
4. High recrystallization volume.
5. High capital cost investment.
D] Di-hydrate Hemihydrate Process
Process description:
In this process, although the reaction runs under di-hydrate conditions, it is not
desirable to affect a very high degree of P2O5 recovery, during the separation of the
acid from di-hydrate. The succeeding dehydration stage requires around 20%-30%
P2O5 and 10%-20% sulphuric acid. The strength of product acid is 32%-35% P2O5.
The sequence is as follows:
i.
ii.
Separate product.
iii.
iv.
Advantages:
1. Flexible as to rock source.
2. Proven process.
3. Produces a pure hemihydrates.
4. High P2O5 efficiency (98%)
5. Higher acid strength [32%-36% P2O5]
6. Lower sulfuric acid consumption.
7. Gypsum may be used directly for plaster board or as a cement retarder, after
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Process description:
Phosphate rock is ground to 20 mesh screen and fed into a dissolver where an acid
stream of conc. HCl plus make up wash water from the counter current decantation
system is added. Fumes of CO2, HF, HCl are scrubbed for acid recovery.
The mixture is fed to series of decantation units with overflow from the first settler
moving to the counter current solvent extraction operations. The solid underflow goes
to 2-3 washing thickners.
Extraction of H3PO4 plus some free HCl is done in a battery of mixer settlers (a) with
CaCl2 + CaF2 retained in aqueous phase. The extract is again passed through several
more mixer settlers (b) for removal of trace impurities of Ca++ which are co-extracted.
The extractant is aqueous reflux from the next unit transfer extractors (c) where water
extracts H3PO4 and HCl from solvent phase.
The washed solvent is recycled to a final series of mixer settlers (d) where trhe
balance of HCl is extracted from raffinate phase of extractors (a). the acid free brine is
send to steam stripping for solvent recovery. The aqueous acid raffinate from (c) is
separated and concentrated in a triple effect evaporator to give three different
overhead streams:
i.
Alcohol-water overhead flash from the first effect which is condensed and
returned to evaporators (a).
ii.
iii.
Advantages:
1. Advantage of this method is it produces less impurity level in phosphoric acid.
2. Phosphoric acid obtain from this process is >50 wt% P2O5.
Disadvantages:
1. Due to the use fo HCl corrosion problem occurs.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
3] Thermal Process:
A] Using phosphate rock and blast furnace
Reaction:
Ca3(PO4)2 + 3SiO2 + 5C
2P + 5CO + 3CaSiO3
2P + 5CO + 5O2
P2O5 + 5CO2
P2O5 + 3H2O
2H3PO4
85-90% yield
Process description:
Phosphate rock is pulverized and mixed with coke powder and binder is compressed
to 5000 psi resulting into the briquettes. Briquettes are dried and charged along with
sand and additional coke powder from top of the blast furnace. The preheated air
(1000 11000C) is charged from bottom of the blast furnace via tuyere. A tuyere is
cooled copper conical pipe numbering 12 in small furnace and up to 42 in large
furnace through which hot air is blown in to the furnace. Preheated air leads to
burning of briquettes giving temperature rise up to 13700C. The coke acts as reducing
agent as well as fuels. About 760kg of coke is consumed in reduction of phosphate
rock to phosphorous and remaining generates heat by combustion with air. Reaction is
completed in the furnace itself producing P2O5 and calcium silicates as slag. The
product gases also contain carbon monoxide and nitrogen along with dust particles.
For purification, it is passed through cyclone separator and phosphorous condenser.
Thus, P2O5 and elemental phosphorous are separated out. Hot P2O5 gases are cooled
in the heat exchanger. Therefore, superheated steam is produced and a part of gas is
taken into regenerative blast furnace. As a result the entire phosphorous and
phosphorous pentoxide is cooled and purified before taken into hydrating towers.
Purification of phosphoric acid includes removal of arsenic by hydrogen sulfide
treatment followed by filtration.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
2P + 5CO + 3CaSiO3
2P + 5CO + 5O2
P2O5 + 5CO2
P2O5 + 3H2O
2H3PO4
85-90% yield
H= -364.8 kcals
H = - 44.9 kcals
Process description:
The phosphate rock is reduced to elemental phosphorous by the action of coke and
heat in the presence of sand in electric arc furnace subsequent oxidation of
phosphorous gives phosphorous pentoxide which on hydration gives the product
phosphoric acid.
Phosphate rock after proper grinding and primary purification is taken into sintering
oven where it is nodulized and granulized so that fast oxidation of the separated
phosphorous takes place. Temperature of 1095 0C is maintained in electric furnace so
that maximum amount of elemental phosphorous extracted out and oxidation takes
place. Since fluoride of phosphorous and calcium are the common impurity which
reacts with sand giving flourosilicates as the slag.
The gases from the furnace, phosphorous and carbon monoxide are removed by the
suction process and the oxidation product P2O5 is taken into hydration column which
gives P2O5 to H3PO4 at about 85 0C. Purification of phosphoric acid is carried out by
H2S to remove Arsenic, H2SO4 to remove calcium salts and Silica to remove
fluorides. All the byproducts are removed before concentrating the acid and filtering it
as final product.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
P2O5 + 3H2O
P 2 O5
2H3PO4
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Process description
At the locations away from phosphate rocks mines from purified elemental
phosphorous is oxidized and hydrated to give phosphoric acid. In the manufacturing
process molten phosphorous is sprayed into combustion chamber along with
preheated air and superheated steam. Combustion of phosphorous increases the
temperature up to 1980 0C. Furnace design depends on the requirement with respect to
quantity and quality. They are made of acid proof structural bricks, graphite, carbon
and stainless steel.
Process flow diagram:
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Process description:
When phosphate rock is treated with nitric acid, it forms phosphoric acid and soluble
calcium nitrate. Rock phosphate is crushed in ball mill. Acidulation of crushed rock
phosphate is processed in reaction vessel by using 40%-70% concentrated nitric acid.
The reaction temperature is 120 0C- 130 0C and the reaction time ranges from 1-2.5
hrs crystal of calcium nitrate are form along with phosphoric acid. These crystals are
separated from phosphoric acid by using filtration. Phosphoric acid is concentrated in
evaporator. The product phosphoric acid contains 55%-72% P2O5.
Advantages:
1. For manufacturing of phosphoric acid wet process are more popular due to
increase demand for higher grade fertilizer
2. It is energy saving process as comparison with thermal process
3. Less expensive process as comparison with thermal process
Disadvantages:
Though thermal process is expensive but it gives extremely pure phosphoric acid, but
this process produces phosphoric acid of 55%-72% P2O5.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
No process
Phosphoric P2O5
Energy
By-product
di-hydrate
29 crore
26%-32%
94%
125 KWH
60% gypsum
Hemihydrate
31 crore
40%-52%
98.5%
110 KWH
95% gypsum
Di-hydrate - 31 crore
32%-36%
98%
110 KWH
95% gypsum
- Di-hydrate
3
Hemihydrate
4
Hemihydrate
25 crore
40%-52%
40% gypsum
Hemihydrate
30 crore
30%-32%
97%
115 KWH
80% gypsum
rock 35 crore
70%-72%
95%
250 KWH
Insoluble
recrystallization
6
Using
phosphate
CaCl2
and HCl
7
Using
rock 45 crore
85%
NA
Over 85%
NA
85%-87%
NA
65%-72%
Ca(NO3)2 as
phosphate
and
electric
furnce
8
Using
rock 42 crore
phosphate
and
blast
furnce
9
By oxidation 45 crore
and
hydration of
phosphorous
10
Using
rock 35 crore
phosphate
waste
HNO3
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
1.5% (max)
CaO
52% (max)
P2O5
33% (min)
SO3
1.4% (max)
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Case2: when 64% sulfuric acid is available from HNO3 concentration plant, it is fed
to head tank. Acid would be drawn at constant rate by the flow controller and fed to
sulfuric acid mixing vessel. Where in it get mixed with the 98% sulfuric acid. Amount
of dilution water required to obtain 75% sulfuric acid are mixed and cooled in dilution
cooler, similar to case 1.
b) Return acid system:
The temperature of return acid in the return acid calibration tank is regulated by the
flow ratio of steam by premixer temperature recording controller.
The return phosphoric acid is adjusted to a designated level of P2O5 concentration i.e.
18%-21% P2O5 and metered within a accuracy of 0.5% by flow controller before
feeding to the premixer through mixing vessel.
The return acid contains dissolved or supersaturated SiO2, CaSO4.2H2O and the
temperature of acids is about 450C 500C under the normal conditions when this
return acid is mixed with the hot sulfuric acid (80 0C). the temperature of resultant
mixed acid is between 60 0C 75 0C. The solubility of gypsum in the consequently
solid gypsum is separated from the mixed acid.
Operating conditions for sulfuric acid & return acid:
i) Concentration of sulfuric acid fed:
75% sulfuric acid in case 1
72.5% sulfuric acid in case 2
ii) Concentration of return acid:
18% -21% with permissible deviation in the concentration from the actual operating
design 0.5% range.
iii) Temperature control:
In case 1, the temperature of diluted sulfuric acid is controlled by adjusting flow rate
of cooling water to the sulfuric acid dilution cooler automatically and set of
temperature control adjusted so that to maintain the temperature of premixer at
designated level.
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In case 2, the temperature of premixer controlled by adjusting flow rate of steam into
return acid calibration tank automatically and the index of temperature controller
should be set at the designated temperature.
IV] Premixer and Digester Section:
Dilute sulfuric acid and the return acid enter the mixing vessel with agitator which
ensures adequate mixing of acids. The mixed acids enter the premixer along with rock
phosphate through screw conveyor and whole mass is agitated by the agitator. The
phosphoric acid and the hemihydrates gypsum is formed in premixer and digestor
under carefully controlled conditions of reaction.
This condition associated with the following factors, individually and in combination:
a) Reaction temperature
b) Combination of sulfuric acid and P2O5 concentration of acid mixture
c) % Decomposition of phosphate rock attained under these stage
d) SO3 / CaO ratio of the slurry
e) The total retention time in this stage i.e. the reaction time
Factors a and b individually or in combination have significant effect on the proper
formation of hemihydrates calcium sulfates. The temperature condition of 90 0C 920C (2 0C) is the optimum temperature in the premixer and digestor. Factor c under
the decomposition stage, a certain minimum % of P2O5 in the rock phosphate must
become water soluble. This % defined by the formula,
% decomposition = [ 1- { [(A-B)/C] / [X/Y] } ] * 100
Where A = total P2O5 in Gypsum cake
B = water soluble P2O5 in gypsum cake
C =totalCaOingypsumcake
X = total P2O5 in phosphate rock
Y = total CaO in Phosphate rock
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The objective of the factor of the process is for high P2O5recoveryand the production
of quality gypsum.
Factor d, the SO3/ CaO ratio of the slurry also influences the formation of large, well
shaped crystal of gypsum.
Factor e, the total retention time in the decomposition stage is associated with the
stability of hemihydrate gypsum. The Nissan process requires hemihydrates gypsum
should be formed in this stage. The hemihydrate stage should be transient stage which
is
followed
by
formation
of
dehydrate
gypsum
through
hydration
and
recrystallization.
Operating conditions:
a) Temperature of slurry in premixer: 90 0C (accuracy of temperature control 2 0C)
b) Temperature of slurry in digestor: 90 0C (accuracy of temperature control 2 0C)
c) Decomposition % of Rock phosphate: 80%-90%
d) Hydration ratio of CaSO4 : 0.5 0.7
e) Temperature controller:
The temperature of the premixer controlled by the aid of the temperature recording
controller by varying the temperature of the feed sulfuric acid in case 1.
In case 2, the temperature of premixer is controlled by the aid of temperature
recording controller by varying the temperature of the feed return acid. The
temperature of the digestor should be kept at 90 0C- 98 0C by regulating the volume of
draught air effecting surface cooling of the slurry in these tanks.
V] Crystallization Section:
The slurry through the last digestor processed through the three crystallizers in series.
These vessels are agitated and connected by launders and here the hydration and
crystallization of the gypsum is complete. The slurry is air cooled by an air blower,
duct work and dispatches into each crystallizer. The slurry from the third crystallizer
is collected in slurry pumping tank by slurry transfer pump to the filter feed splitter
box, back to number 1 crystalleizer where it helps cooling and crystallization.
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Slurry is also metered to filter and the excess over flows back to number 3
crystallizer. The total volume and the distribution of air to each crystallizers are
controlled by dampers on air lines. Fumes are removed from the crystallizers by two
numbers of exhausts fans and passed to atmosphere through the exhausts stack. The
pressure in each crystallizer is kept slightly negative. The temperature in the
crystallizers is controlled to maintain optimum declining temperature gradient for recrystallization and hydration. It is removed by temperature recorder.
The solubility of calcium sulfate in its hemihydrate state rises rapidly with the drop in
the temperature. The solubility of the di-hydrate calcium sulfate with maximum at
about 50 0C is for less than hemihydrate in the crystallization stage, the slurry of
relative high temperature containing hemihydrate calcium sulfate is cooled to a
temperature below the hemihydrate di-hydrate transition point. Solubility of
hemihydrate increases considerably.
In the actual operation of Nissan process, however, the solubility difference does not
act directly as a motive force. The recrystallization of the hemihydrate to di-hydrate is
dependent not only on the temperature but also on the ratio of the recycled feed slurry
and the ratio of the recycled feed slurry and the ratio of new slurry feed respectively
to slurry retained on the crystallizer. The actual motive force promoting the
recrystallization is subject to the degree of super saturation of di-hydrate gypsum. The
hydration and crystallization are frequently influenced by minor constituents of the
rock phosphate, such as metallic sesquioxides, SiO2, fluorine and organic matter. As it
is apparent considerable hydration heat is generated in this stage, necessiting a fairly
large quantity of heat to be removed. This is accomplished in practice by air cooling,
in the crystallization stage, the following factors are to be considered:
1. Retention time
2. Hydration temperature
3. Recycle ratio of feed slurry
4. Free sulfuric acid content in filtrate acid
Most important factor in the Nissan process can be said to be the retention time. The
term retention time is defined as the average retained time of the slurry in series of
reaction vessels ignoring the effects of such recycle. This is expressed as:
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Q=V/F
Where,
Q = Retention time
V = Effective volume of crystallizer
F = feed rate of slurry from the decomposition
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Crystallizer no 1: 63 0C
ii.
Crystallizer no 2: 58 0C
iii.
Crystallizer no 3: 53 0C
iv.
Crystallizer no 4: 53 0C
b) Decomposition %:
Minimum: 98% (for Algeria and Tunisian rock)
98.5% (for Morocco, Jordan, Florida rock)
c) Hydration ratio: 1.90
d) Slurry recycle ratio: 1:1 to 2:1
VI] Filtration Section:
The phosphoric acid and the gypsum are separated by filtration using horizontal
vacuum belt filter. The slurry from the crystallizer containing phosphoric acid along
with the di-hydrate gypsum is passed to slurry pumping tank. The tank is cylindrical
with the agitation, completely lined vessel of the size 4500 mm *4000 mm height
having hold up capacity 56 m3. Slurry pumping tank pumps the slurry to filter feed
splitter box. The filter feed splitter box is a vertical rectangular type of size 1500mm *
1200 mm * 1100 mm (l*b*h) having hold up capacity of 0.4 m3.
The purpose of the splitter box is to maintain uniform flow rate of hydrated slurry to
the filtration unit and excess supply of the slurry is fed back to the crystallizer. The
filter used is horizontal vacuum belt filter, having effective filtration area is 29 m2.
The slope of filtration unit is 0.6%, so adjusted in such way that the discharge end of
the filter is slightly higher than the feed end. The vacuum is created by barometric
condenser in the downstream which results into suction of phosphoric acid from
gypsum is collected into three receivers.
The phosphoric acid from the first receiver having 30% P2O5 acid is pumped to the
clarifier and the phosphoric acid from the second receiver having 18% - 20% P2O5 is
sent to the return acid tank. Phosphoric acid from third receiver is having 5% P2O5 is
sent to 1st acid wash of the gypsum. The liquor passed from all the sections of the
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
filter under vacuum i.e. slurry feed acid wash, water wash, cake drying, cloth drying
section all have entrained in them. The air from the filtrate separator on the slurry feed
acid wash and the water wash sections of the filter passes to primary spray condenser
which removes any acidic vapours that may be in the air by scrubbing with process
water.
The decontaminated air then enters the primary vacuum pump. A similar arrangement
applies for the cake drying section of the filter which has its own separator and
secondary spray condenser and it is connected to secondary vacuum pump. The
process water leaving the scrubber and passes to the sealed tank respectively for
disposal.
Principal of washing of filter cake:
1) The washing effect is dependent mainly on two factors below under the conditions
of cake thickness of the vacuum applied being considered to be constant. These
factors are E, displacement efficiency and n is washing ratio. Washing ratio is
defined as :
n = (volume of washing fluid) / (volume of liquor cake)
Displacement efficiency E is defined as % of soluble matter washed of the filter cake
to the total soluble matter before washing ratio n = 1, is assumed to be applied and
this factor E is characteristic to the filter cake itself in gypsum cake washing, this
depending on crystal size, uniformity of crystals size distribution etc.
Taking the remaining ratio of the soluble matter in the cake as R is given as follows:
R= { 1 [E/100] }^n
Where R = remaining ratio of soluble matter in the cake
E = displacement efficiency
n = washing ratio
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
CHAPTER NO 6:
THERMODYNAMICS AND REACTION KINETICS
A] THERMODYNAMICS
Introduction
Thermodynamics is a branch of physics concerned with heat and temperature and
their relation to energy and work. Thermodynamics checks the feasibility of the given
reaction by using Gibbs Free energy. Gibbs free energy can be calculated by using
following formula:
G = H - TS
.[A]
Significance:
1. If G is negative then, the proportion of products present will be large.
2. If G is positive then, the proportion of products present will be small.
3. If G is zero then, there will be equal proportion of products and reactants.
4. If G is more negative than -40kJ/mol then, the reaction is regarded as having
gone to completion.
5. If G is more positive than about +40kJ/mol then, the reaction is regarded as
not occurred at all.
The formation reaction of phosphoric acid by hemihydrate- dihydrate process (Nissan
Process) using sulfuric acid and rock phosphate is as follows:-
(2)
Where reaction (1) is carried at 920C in premixer and digester and reaction (2) is
carried out at 570C in crystallizers.
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Calculations
1. Standard values (at 250C) of heat of reaction(Ho) and entropy (So) for all
component presents in the given reactions is given below:
Components
Hfo(kJ/mol)
So(kJ/mol)
1.
Ca3(PO4)2CaF2
-1506.88
0.19056
2.
H2SO4
-814
0.1569
3.
H 2O
-258.83
0.06991
4.
H3PO4
-1254.36
0.15062
5.
CaSO4.1/2H2O
-1576.74
0.13054
6.
HF
-271.12
0.173.68
7.
CaSO4.2H2O
-2022.63
0.19414
Sr.
No.
2. Data of specific heat capacity (Cp) for all the component present in the
reaction is as follows:
Components
.dT
Cp. dT
Temperatures
920C
570C
920C
Ca3(PO4)2CaF2
-0.1873
0.1665
0.028
570C
0.0164
-3
H2SO4
0.1315
0.0628
2.5510
H2 O
2.3092
1.1022
0.0107
1.61710-3
0.0067
-3
H3PO4
0.00221
0.00105
0.04310
0.02710-3
CaSO4.1/2H2O
-0.01671010
-0.003711010
-614103
-205103
HF
2.967103
-1.067103
-12.4
-6.25
CaSO4.2H2O
13.063
6.239
0.254
0.16
3. Heat of reaction (Hf) can be calculated at any temperature using the formula:
Hf
= Hf
Cp. dT
(3)
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.dT
(4)
= S0product - S0reactant
= -8.6210-3 kJ/mol
.dT =
.dTproduct -
.dTreactant
= -6.14106 kJ/mol
From equation (4),
S = -8.6210-3 + -6.14106
S = -6.14106 kJ/mol
Similarly, for reaction (2)
S = 0.409106 kJ/mol
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From the value of Gibbs Free energy of both the reactions, we conclude that both
reactions are feasible and goes to completion.
B] REACTION KINETICS
Introduction
The formation reaction of phosphoric acid is completed in two steps. The first step is
the first peak to dissolution of Fap and neutralization H2PO4- into H3PO4, and the
second step to precipitation of CaSO4.1/2H2O according to the following reaction:
For First Peak Reaction
Ca10(PO4)6F2(s) +20{H+}sol {10Ca+2 + 6H3PO4 + 2HF}sol
1st step
2nd step
With mean iteration enthalpy values as -15.0 and --12.0 kJ per mole of Ca-sulfate,
respectively.
For Second Peak
CaSO4.0.5H2O(s) + 3/2 H2O CaSO4.2H2O(s)
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The dissolution rate of HH, rdis, is proportional to under saturation (Ce [Ca]) where
Ce is the Ca concentration corresponding to solubility of HH, whereas precipitation
rate of DH, rpp, is of order rate 2 for Ca concentration, and so,
rdis = k1(Ce [Ca2+]) and
..(1)
rpp = k2 [Ca2+]2
..(2)
..(4)
..(5)
(6)
..(7)
..(8)
Let Q1 and Q2 denote the heat quantities released by hemihydrate dissolution and
dehydrateprecipitation reactions respectively. Variation of each of these quantities is
proportional tothe corresponding reaction rate as,
dQ1/dt = VdisHk1(Ce [Ca2+]) and
..(9)
dQ2/dt = VppHk2[Ca2+]2
...(10)
With disH and ppH the molar enthalpies of dissolution of HH and precipitation of
DH, respectively.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
(11)
.....(12)
After performing the iterations on these expressions, we obtain the following values
of six parameters,
Hdis = 12.30 kJ/mol, Ce = 3.2710-4mol/L
Hpp= -24.90 kJ/mol, C2 = 59.33
We obtain,
k1 = 5.0010-5 s-1
{reaction (1)}
k2= 1.9910-3L/mol.s
{reaction (2)}
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Premixer/
digestor
Separation
byfilter
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3 kmoles of [Ca3(PO4)2CaF2]
? kmoles of [Ca3(PO4)2CaF2]
.
ii.
10 kmoles of H2SO4
? kmoles of H2SO4
.
iii.
= 117.167 kmoles/hr
5 kmoles of H2O
? kmoles of H2O
.
iv.
= 58.583kmoles/hr
10 moles of CaSO4.1/2H2O
? kmoles of CaSO4.1/2H2O
v.
= 35.15 kmoles/hr
= 117.167kmoles/hr
2 moles of HF
? kmoles of HF
= 23.433kmoles/hr
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Therefore,
Total Mixed Feed (M) = kmoles of [Ca3(PO4)2CaF2] + kmoles of H2SO4
+ kmoles of H2O
= 35.15 + 117.167 + 58.583
= 210.9 kmol/hr
Now, recycle ratio ( ) = 1 : 1
Therefore, R= F
Overall material balance,
M = R+ F
Therefore, M = 2F
F=
= 210.9/2 = 105.45kmol/hr
Therefore, R = F = 105.45kmol/hr
Actual amount of fresh feed required:
Basis:- 105.45kmol/hr of fresh feed,
The proportion of feed is,
Ca3(PO4)2CaF2 : H2SO4 : H2O = 3: 10: 5
Amount of [Ca3(PO4)2CaF2] =
Amount of H2SO4 =
= 31.635 kmol/hr
= 52.725 kmol/hr
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
UNIT
MATERIALS
PREMIXER
INPUT
OUTPUT
(kmol/hr)
(kmol/hr)
Ca3(PO4)2CaF2
31.635
--
H2SO4
52.725
--
H2 O
21.09
--
RECYCLE FEED
105.45
--
H3PO4
--
70.3
CaSO4.1/2H2O
--
117.167
HF
--
23.433
TOTAL
210.9
210.9
CRYSTALLIZER
F
3 moles of H2O
? kmol of H2O
= 175.75kmol/hr
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
ii.
2 moles of 2CaSO4.2H2O
? kmol of 2CaSO4.2H2O
.
= 117.167kmol/hr
MATERIALS
INPUT (kmol/hr)
OUTPUT (kmol/hr)
CaSO4.1/2H2O
117.167
--
H 2O
175.75
175.75
--
117.167
292.917
292.917
CaSO4.2H2O
TOTAL
For material balance in kg/hr
Basis: 6890kg/hr of H3PO4 leaving
UNIT
MATERIALS
INPUT (kmol/hr)
OUTPUT(kmol/hr)
Ca3(PO4)2CaF2
15564.42
---
H2SO4
5167.05
---
H2 O
379.62
---
PREMIXER/
RECYCLE FEED
2954.989
---
DIGESTOR
H3PO4
---
6889.4
CaSO4.1/2H2O
---
16989.215
HF
---
187.464
TOTAL
24066.079
24066.08
CaSO4.1/2H2O
16989.215
---
H2 O
3163.5
2108.997
CaSO4.2H2O
---
18043.718
TOTAL
20152.715
20152.715
CRYSTALLIZER
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B] HEAT BALANCE
Introduction
The basis of energy balance of the system is the low of conservation of energy, which
states that energy can neither be created nor be destroyed during a process, although it
can be converted from one form to another and the total energy of an isolated system
remains constant. This law is also called as first law of thermodynamics.
For closed system, the energy balance equation is,
[Final system energy] [Initial system energy]= [Net energy transferred by system]
General procedure for energy balance:
1. Assume a suitable basis of calculation.
2. Draw a block diagram of the process and lable the stream.
3. Determine the quantity of flowrates of all components with the help of
material balance.
4. Determine the enthalpy of each stream components entering or leaving.
5. If a chemical reaction is involved where in heat is evolved or absorbed, it must
be included in the energy balance equation.
6. If the heat capacity data is provided for component involved, choose a
reference temperature on which they are based for the convenience of
calculation.
Energy Balance Calculation:
Heat capacity Cp (J/mol.K) is calculated at average temperature using these formulas.
Sr. No.
COMPONENTS
Cp value
1.
Ca3(PO4)2CaF2
2.
H2SO4
0.4628 cal/g.K
3.
H2 O
4.
H3PO4
0.7735 cal/g.0C
5.
CaSO4.1/2H2O
6.
HF
7.
CaSO4.2H2O
46.8 cal/mol.K
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
363K
365K
326K
331K
336K
Ca3(PO4)2CaF2
55.3536
55.578
51.3192
51.8652
52.4112
H2SO4
4.72210-3
4.72210-3
4.72210-3
4.72210-3
4.72210-3
H2 O
671.035
671.689
650.118
653.948
657.484
H3PO4
7.8910-3
7.8910-3
7.8910-3
7.8910-3
7.8910-3
CaSO4.1/2H2O
75.7728
75.7708
74.2708
74.4708
74.6957
HF
2.081
2.552
-5.720
-4.766
-3.781
CaSO4.2H2O
195.624
195.624
195.624
195.624
195.624
I.
Premixer:
The energy balance around a premixer is based on the following chemical reaction:
3Ca3(PO4)2CaF2 + 10H2SO4 + 5H2O 6H3PO4 + 10CaSO4.1/2H2O + HF
To calculate Q:
Q
[Hproduct - Hreactant]
Hproduct
Hreactant
H (enthalpy) =
mCpdT
= mCp(365 298)
= mCp(67)
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Rate In
Rate out
(kg/hr)
(kg/hr)
Ca3(PO4)2CaF2
15564.42
H2SO4
Component
Cp (363 K)
H(enthalpy)
---
55.3536
57.72106
5167.05
---
4.72210-3
1634.720
H2 O
379.62
---
671.035
17.067106
H3PO4
---
6889.4
7.8910-3
3641.94
CaSO4.1/2H2O
---
16989.215
75.7728
86.247106
HF
---
187.464
2.081
26137.54
Recycle feed
2954.989
---
1.23
0.243106
Hproduct
86.276106 J/kg
Hreactant
75.061106 J/kg
(86.276106) (75.061106)
Qheat
11.215103 kJ/kg
II.
Digester:
PREMIXER
Rate Out
Cp (365K)
(kg/hr)
(kg/hr)
J/mol.K
Ca3(PO4)2CaF2
15564.42
---
55.578
1.73106
H2SO4
5167.05
---
4.72210-3
48.7976
H2 O
379.62
---
671.689
0.5099106
H3PO4
---
6889.4
7.8910-3
7151.073
CaSO4.1/2H2O
---
16989.215 75.7708
108.7147
HF
---
187.464
2.552
2.574106
Recycle feed
2954.989
---
1.21
956.816
Component
H(enthalpy)
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Hproduct
2.575106 J/kg
Hreactant
2.247106 J/kg
(2.575106) (2.247106)
Qheat
0.328103 kJ/kg
III.
DIGESTER
Rate out
(kg/hr)
(kg/hr)
CaSO4.1/2H2O
16989.215
H 2O
CaSO4.2H2O
Component
Cp (326K)
H(enthalpy)
---
74.2708
-49.21106
3163.5
---
650.118
-80.209106
---
18043.718
195.624
-137106
Hproduct
-137106 J/kg
Hreactant
-49.21106 + -80.209106
-129.419106 J/kg
(-137106) (-129.419106)
Qcool
-7.581103 kJ/kg
st
1 crystallizer
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
VI.
Rate out
(kg/hr)
(kg/hr)
CaSO4.1/2H2O
16989.215
H 2O
CaSO4.2H2O
Component
Cp (326K)
H (enthalpy)
---
74.4708
6.326106
3163.5
---
653.948
10.343106
---
18043.718
195.624
15.64106
Hproduct
15.64106 J/kg
Hreactant
6.326106 + 10.343106
16.669106 J/kg
(15.64106) (16.669106)
Qcool
-1.029103 kJ/kg
The amount of heat to be removed from 2nd& 3rd crystallizer is 1.029103 kJ/kg.
Hreactant= 16.669106 J/kg
V.
Rate out
(kg/hr)
(kg/hr)
CaSO4.1/2H2O
16989.215
H 2O
CaSO4.2H2O
Component
Cp (326K)
H (enthalpy)
---
74.6957
6.345106
3163.5
---
657.484
10.39106
---
18043.718
195.624
15.648106
Hproduct
15.648106 J/kg
Hreactant
6.345106 + 10.39106
16.735106 J/kg
(15.64106) (16.735106)
Qcool
-1.087103 kJ/kg
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
4th crystallizer
Hproduct=15.648106 J/kg
Qtotal
Therefore,
Qtotal
0.817103 kJ/kg
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Product size
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
L = 85.71 25 1854
= 3996.75mm = 3.99675m = 13.11ft 14ft
For designing purpose we consider 10% excess length for suitable grinding
condition
L = 1.1 14 = 15.4ft
Consider length of ball mill
L = 16ft
2. Diameter of Ball
Db =
Where,
Db = diameter
Pf = size in of 80% passing in the fresh feed
C = 200 for ball mill
Wi = work index
Vcr = percentage of critical speed
Sgs = specific gravity of feed
D = internal diameter of mill in m
By substituting all the values, we get,
Db = 42.72mm
Ball mill run at 65% of critical speed
For designing purpose we consider ball diameter is 50mm and 40mm
Db = 50mm and 40 mm
3. Number of Balls:
Volume of ball mill = 122 16
= 1809.55ft
Bulk volume of balls charge ratio to the volume of mills is known as filling
ratio (F) and its range is 30- 45%. Assuming filling ratio to be 35%.
Therefore, F =
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
c=
c=
.
.
c= 0.3709 rps
c= 22.25 rpm
Operating speed is (65%) of critical speed
= 0.65 c
= 0.65 22.25
= 14.46 rpm
For balls we take alloy steel is IS-6079 as material of construction. Therefore total
weight of balls is 61.7tonnes.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
P = 478530.10kW
P =641708.86 HP
6. Thickness of ball mill;
t=
Where, P = design pressure
Di = internal diameter
J = joint efficiency
f = design or permissible stress at design temperature
Assuming internal pressure P = 0.3 N/mm2
Therefore, design pressure, p = 0.3 1.1 = 0.33N/mm2
Allowable stress at 300C = 30N/mm2
t=
.
.
t = 23.82mm
t 25 mm
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
B] DESIGN OF PREMIXER:
Data:
Type cylindrical with agitation, completely lined vessel
Agitator type anchor agitation
Size of vessel 2275mm ID 1465mm liquid height
Hold up capacity 5.95m3
Agitator rpm(N) 120
Operating conditions:
Temperature 900C
Pressure hydrostatic
M.O.C carbon steel with butyl rubber lining + carbon brick lining
Function to mix up completely rock phosphate with sulfuric acid and phosphoric
acid
Diagram:
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
=
To calculate,
f =
(2)
Component
m (kg/hr)
v (kg/hr)
1.
H2 O
379.62
0.3796
2.
H2SO4
5167.05
2.808
3.
Return acid
2954.989
8.2351
4.
Rock phosphate
15564.42
8.833
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Tr =
Tr = 162.45 N-m
Maximum torque for design, Tm
Tm = 1.5 Tr
= 1.5 162.45
Tm = 243.686 N-m
Design of shaft based on pure torsion,
Tm =
d3 fs
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
= 23866.973
d3 =
Therefore, d= 28.7910-3m
Design of shaft based on pure bending
a) Fm = Tm/(0.75Rb)
Where Fm = bending force
Rb = radius of impeller
Therefore, Fm = 243.686/(0.751.02375)
Fm = 317.376 N-m
b) Mm = Fm l
Where, Mm= maximum bending moment
l = length of shaft
= 730mm {assumed}
Mm = 317.376 0.73
Mm = 231.684N-m
c) Mm =
fb d3
d3 = Mm32/( fb)
d = 21.4210-3m
Design based on equivalent twisting moment,
Te =
Te = 336.244 N-m
Te =
52 d3
Therefore, d = 3210-3m
Design based on equivalent bending moment
Me = (Mm +
= (231.684 + 336.244)
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
240 d3
Me =
d = 22.927 10-3m
selecting the maximum diameter of shaft as 32mm
Design of shaft based on critical speed,
Actual speed should not be between 66.6% to 130% of critical speed Nc
Nc = N100/66.6
Nc = 120100/66.6or
Nc = 180.180rpm
Now, Nc = 946/1/2
Where, = appropriate deflection in mm
= 27.565mm
The maximum deflection due to each load acting independently is given by,
=
Weight(W) = mass 9.81
= 0.236 106 N
=
= 27.56510-3
d = 21.4410-3m
Hence selected shaft size is 22mm
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
= lb.fs = l.(t/2).fc
/
.
= 33 b 65 = 33(t/2) 130
b = t = 0.0103mm
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
+ 6mm
.
+6
Therefore t = 6.09mm
Load on glands,
F = P(d12 d22) = db2 n ft
Therefore, db = 1.6mm
Use minimum stud diameter as 16mm and 4 no. of studs.
Thickness of stuffing box flange = 1.75 db
= 1.75 1.6
Therefore,
ts= 28mm
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Process Type
Suitable equipment
Rapid filtering
0.1-10 cm/sec
Medium Filtering
0.1-10 cm/min
Slow filtering
0.1-10 cm/hr
Clarification
Negligible cake
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Area Of Filtration:
C = It is solid concentration per unit volume of filtrate = wt. of solid/volume of liq
C = 9754.33/(62500/1638)
C = 255.64 Kg/m3
Cx = kg of solids per kg of slurry = 0.2986/202123
Cx = 0.135
Feed rate = 2.2123 Kg/sec
Flow rate of filtrate
V/tc = Feed rate*(Cx/C) = 2.2123*(0.135/255.817)
V/tc = 101685*10-3 m3filtrate/sec
V/Atc = (2*P/Ctc)0.5
P = pressure drop = 80,000 Pa
= filtrate viscosity = 0.02 Ns/m2
= (4.37*109)*(P)0.3 = (4.37*109)*(80,000)0.3
= 1.2924*1011m/kg
sp. surface area of cake (So) =16077.31 m2
tc = filter cycle time = 90sec
V/Atc = (2*P/Ctc)0.5
101685*10-3/A = (2*80,000/90*0.02*1.2924*1011*255.5817)0.5
A= 25.6317 m2
Area for filtration should be 25-30 m2
Rate Of Filtration
Q=A*P/*[Rf+(C**V/A)]
Rf = cake thickness/permeability for fine filter sheet
Rf = 6.833*10-6/0.15*10-12 = 4.555*107
Q = 25.6317*80,000/0.02*[(4.555*107)+(255.5817*1.2924*1011*100.94/25.6317)]
Q = 8.1099*10-7 m3/sec
Q = 2.9195 lit/hr
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
oxidizing agents (iron & copper). They have been the materials of choice in
some high temperature organic synthesis under reducing conditions.
5. Nickel & its alloy:
Chromium free alloys N02200 &N04400 are of small use in phosphoric acid,
being less resistant than copper alloys under reducing condition &attacked
under oxidizing conditions. The Molybdenum grade N10665 will resist pure
acid of all concentrations to about 65C & up to 50% in atm boiling points. It
is however rapidly corroded by oxidizing contaminants. Alloys of primary
interest are the specialty alloy N06007 & 6% molybdenum stainless steel alloy
31(N08031). These were developed specially for wet process phosphoric acid
6. Reactive Metals:
Titanium: because it is not a oxidizing acid phosphoric acid tends to attak
titanium zirconium: zirconium resist pure acid to about 50% concentration,
and above the atmospheric boiling temperature, but corrosion rates increases
sharply above about 60% at 100C fluorides, zirconium equipment has been
used to process a phosphoric acid-containing medium.
Tantalu : It will resist all concentrations of phosphoric acid to about 190Cif
there is not more than a small fluoride concentration
Niobium: Niobium resists phosphoric acid up to 95% & up to 60C
7. Noble Metals:
Gold and platinum will resist all concentration of pure acid to the atmospheric
boiling point silver corrosion rate increase from less than 1mpy in 15%acid at
the atmospheric boiling point to 2mpy in 60% and 7mpy is 85% up to 250C
(480 F)
8. Non-Metals:
Organic: In the absence of solvent contamination conventional plastic, PVC,
polyethylene, epoxyphenolic resist all concentration to the inherent
temperature limitof the plastic. Troweled epoxy coatings are used to protect
concrete tank padsfromacid spillage. The fluorinated plastics are resistant to
higher temperature.
Inorganic: Carbon & graphite are inert in all concentrations of acidwith or
without contaminants to at least 350C. A film of phosphate protects against
oxidation. Some impervious graphite products are limited to about 170C by
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
ii.
iii.
Utilities Cost(UC)
iv.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Depreciation cost(DC)
ii.
TCI = FCI+WC
TCI = FCI+ 0.2TCI
Therefore
2. TOC = FCC+WC
3. NET PROFIT = (Gross Income -Taxes)
Gross Income = Total Income Total Product Cost
Where,
Total Income = (Selling price Quantity of product manufacturing)
4. RATE OF RETURN (ROR):
ROR =
TOC /(Profit+Depreciation)
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
CALCULATIONS:
Direct cost:
a) To calculate purchased equipment cost (PEC):
COST (in `)
Sr No.
EQUIPMENT
22,39,060
3,09,506
3,28,760
6,12,600
62,000
64,680
3,61,136
29,70,680
4,14,120
10
48,980
11
36,95,870
12
1,01,522
13
77,380
14
Storage Tank
42,340
` 11.28106 /-
b) IC = 30% OF PEC
IC = 0.311.28106
IC = `30384106 /c) ICC = 15% OF PEC
ICC = 0.1511.28106
ICC = ` 1.692106 /d) PC = 20% OF PEC
PC = 0.211.28106
PC = ` 2.252106
/-
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
e) EC = 20% OF PEC
EC = 0.211.28106
EC = ` 2.252106 /-
DIRECT COST
= PEC+IC+ICC+PC+EC
=(11.28+3.384+1.692+2.256+2.256)106
DIRECT COST
= `20.868106/-
Indirect Cost:
a) E&SC = 20% OF Direct cost
E&SC = 0.220.868106
E&SC = ` 4.1736106/b) CE&CC = 30% of E&SC
CE&CC = 0.34.1736106
CE&CC = ` 1.252106/INDIRECT COST = E&SC + CF&CC = (4.1736+1.252)106
INDIRECT COST = ` 5.4256106 /-
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
NET PROFIT:
NET PROFIT = Gross Income Taxes = (22.483 -5.2588) 106
NET PROFIT = ` 17.2242106/-
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
transport of bulk chemicals. Air transport is convenient and efficient for the
movement of personnel and essential equipment and supplies, and the proximity of
the site to a major airport should be considered.
D] Availability of labour
Labour will be needed for construction of the plant and its operation. Skilled
construction workers will usually be brought in from outside the site area, but there
should be an adequate pool of unskilled labour available locally; and labour suitable
for training to operate the plant. Skilled tradesmen will be needed for plant
maintenance. Local trade union customs and restrictive practices will have to be
considered when assessing the availability and suitability of the local labour for
recruitment and training.
E] Utilities
Chemical processes invariably require large quantities of water for cooling and
general process use, and the plant must be located near a source of water of suitable
quality. Process water may be drawn from a river, from wells, or purchased from a
local authority. At some sites, the cooling water required can be taken from a river or
lake, or from the sea; at other locations cooling towers will be needed. Electrical
power will be needed at all sites.
Electrochemical processes that require large quantities of power; for example,
aluminium smelters, need to be located close to a cheap source of power. A
competitively priced fuel must be available on site for steam and power generation.
F] Environmental impact and effluent disposal
All industrial processes produce waste products, and full consideration must be given
to the difficulties and cost of their disposal. The disposal of toxic and harmful
effluents will be covered by local regulations, and the appropriate authorities must be
consulted during the initial site survey to determine the standards that must be met.
An environmental impact assessment should be made for each new project, or major
modification or addition to an existing process.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
D] Maintenance
Heat exchangers need to be sited so that the tube bundles can be easily withdrawn for
cleaning and tube replacement. Vessels that require frequent replacement of catalyst
or packing should be located on the outside of buildings. Equipment that requires
dismantling for maintenance, such as compressors and large pumps, should be placed
under cover.
E] Safety
Blast walls may be needed to isolate potentially hazardous equipment, and confine the
effects of an explosion. At least two escape routes for operators must be provided
from each level in process buildings.
F] Plant expansion
Equipment should be located so that it can be conveniently tied in with any future
expansion of the process. Space should be left on pipe alleys for future needs, and
service pipes over-sized to allow for future requirements.
G] Modular construction
In recent years there has been a move to assemble sections of plant at the plant
manufacturers site. These modules will include the equipment, structural steel, piping
and instrumentation. The modules are then transported to the plant site, by road or
sea. The advantages of modular construction are:
1. Improved quality control.
2. Reduced construction cost.
3. Less need for skilled labour on site.
4. Less need for skilled personnel on overseas sites.
Some of the disadvantages are:
1. Higher design costs.
2. More structural steel work.
3. More flanged connections.
4. Possible problems with assembly, on site.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
H] General considerations
Open, structural steelwork, buildings are normally used for process equipment; closed
buildings are only used for process operations that require protection from the
weather. The arrangement of the major items of equipment will usually follow the
sequence given on the process flow-sheet: with the columns and vessels arranged in
rows and the ancillary equipment, such as heat exchangers and pumps, positioned
along the outside.
SITE SELECTION
The process units and ancillary buildings should be laid out to give the most
economical flow of materials and personnel around the site. Hazardous processes
must be located at a safe distance from other buildings. Consideration must also be
given to the future expansion of the site. The ancillary buildings and services required
on a site, in addition to the main processing units (buildings), will include:
1. Storages for raw materials and products: tank farms and warehouses.
2. Maintenance workshops.
3. Stores, for maintenance and operating supplies.
4. Laboratories for process control.
5. Fire stations and other emergency services.
6. Utilities: steam boilers, compressed air, power generation, refrigeration,
transformer stations.
7. Effluent disposal plant.
8. Offices for general administration.
9. Canteens and other amenity buildings, such as medical centres.
10. Car parks.
General Consideration:
A] When roughing out the preliminary site layout, the process units will normally be
sited first and arranged to give a smooth flow of materials through the various
processing steps, from raw material to final product storage. Process units are
normally spaced at least 30 m apart; greater spacing may be needed for hazardous
processes.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
B] The location of the principal ancillary buildings should then be decided. They
should be arranged so as to minimise the time spent by personnel in travelling
between buildings. Administration offices and laboratories, in which a relatively large
number of people will be working, should be located well away from potentially
hazardous processes. Control rooms will normally be located adjacent to the
processing units, but with potentially hazardous processes may have to be sited at a
safer distance.
C] The siting of the main process units will determine the layout of the plant roads,
pipe alleys and drains. Access roads will be needed to each building for construction,
and for operation and maintenance.
D] Utility buildings should be sited to give the most economical run of pipes to and
from the process units.
E] Cooling towers should be sited so that under the prevailing wind the plume of
condensate spray drifts away from the plant area and adjacent properties.
F] The main storage areas should be placed between the loading and unloading
facilities and the process units they serve. Storage tanks containing hazardous
materials should be sited at least 70 m (200 ft) from the site boundary.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
: N/A
: N/A
Fighting Procedure
Health Hazards
Short term
Long term
Skin
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
lay victim on side with head lower than waist. If vomiting occurs do not readminister water. Do not give anything by mouth to an unconscious person.
e) Immediately obtain medical attention.
3) Fire hazard data:
Flash Point: Not Applicable
Not combustible. Strong oxidizers can react with reducing agents or combustibles
producing heat and causing ignition. Reacts violently with water releasing heat and
corrosive material.
a) Not combustible. Use extinguishing method suitable for surrounding fire.
Recommended (small fires): dry chemical.
b) Firefighters should wear NIOSH/MSHA approved positive pressure breathing
apparatus with full face-piece and full acidresistant protective clothing. Fight
fire from maximum distance.
4) Evacuation Procedures and Safety:
a) Personnel handling this material should be thoroughly trained to handle spills
and releases. Do not direct hose streams into an unignited transportation spill
(tank truck or tank car).
b) Stop leak if it can be done without risk. Dike spill using absorbent or
impervious materials such as earth, sand or clay. Dike or retain dilution water
or water from firefighting for later disposal.
c) Pump any free liquid into an appropriate closed container. Exercise caution
during neutralization as considerable heat may be generated. Carefully
neutralize spill with soda ash. Absorb neutralized spill with an inert absorbent.
Scrape up and place in appropriate closed container.
5) Environmental and Regulatory Reporting:
Do not flush to drain. Runoff from fire control or dilution water may cause pollution.
Dispose of as a hazardous waste. Spills may be reportable to the National Response
Center (800-424-8802) and to state and/or local agencies. Large spills should be
handled according to a predetermined plan.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
3) Fire-fighting measures
Product is not flammable.
a) Use appropriate media for adjacent fire. Cool containers with water, keep
away from common metals.
b) Wear self-contained, approved breathing apparatus and full protective
clothing, including eye protection and boots.
c) Emits toxic fumes under fire conditions.
d) Material can react with metals to produce flammable hydrogen gas. Forms
flammable gases with aldehydes, cyanides, mercaptins, and sulfides.
4) Accidental release measures
a) use of personal protective equipment.
b) Cleanup personnel need personal protection from inhalation and skin/eye
contact. Evacuate and ventilate the area. Prevent spillage from entering drains.
Cautiously add water to spill, taking care to avoid splashing and spattering.
Neutralize diluted spill with soda ash or lime. Absorb neutralized spill with
vermiculite or other inert absorbent material, then place in a suitable
c) Created onrelease to the environment may be subject to federal/national or
local reporting requirements. Dispose of all waste or cleanup materials in
accordance with local regulations. Containers, even when empty, will retain
residue and vapors.
5) Handling and storage
a) Use with adequate ventilation. Wash thoroughly after using. Keep container
closed when not in use.
b) Store in cool, dry well ventilated area. Keep away from incompatible
materials. Drains for storage or use areas for this material should have
retention basins for pH adjustment and dilution of spills.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Control measures for minimizing generation of large quantity and bad quality
effluent:
Measures:
To improve effluent quality:
a) Isolate equipment to be cleaned
b) Recycle slurry to process
c) Dilute the balance slurry with water before draining
d) Checking that foaming is not taking place in filtrate compartments etc. to
prevent acid spillage
e) Ensure antifoam dosing in filtrate compartments etc. in case of foaming
f) Check no leakage is taking place from phosphoric acid, slurry warman pumps,
etc.
g) Isolate pump in case of leakage and inform mechanical maintenance
department for attending leakage
h) Check filter wash system is working in auto mode to prevent acid overflow
from filtrate compartments, return acid tank
i) If filtrate wash system is not working in auto mode then instrumentation
department should be informed
j) Analyzing effluent pH, total phosphate and maintain records
k) Plant effluent is recycled back in process
To reduce in effluent generation quality:
a) Ensure dry cleaning of equipment, floors to minimize effluent generation.
Water is not to be used for cleaning
b) Use only minimum water for final cleaning of equipments if required
c) Transferring the sludge collected from equipment after dry cleaning to
crystallizer to recover P2O5 content from gypsum
Analyze effluent quantity trend and maintain records and take appropriate actions in
case of deviations in quality and quantity of effluents.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
ii.
iii.
iv.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
v.
SEPARATION TECHNIQUE:
a. EVAPORATION UNIT:
i.
ii.
iii.
iv.
ii.
vi.
vii.
ii.
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
iii.
iv.
v.
WORKING:
i.
The process sequence involved emulsifying the aqueous strip phase into an
organic phase containing a surfactant &complexing agents
ii.
The emulsion was then dispersed in aqueous feed phase, which contained
the species to be removed. During this complexing step, the desired
species was transferred & concentrate in emulsified aqueous internal phase
iii.
iv.
ADVANTAGES:
The unique aspects of this technique was that extraction & stripping were affected
simultaneously than sequentially in conventional solvent extraction
3. ENVIRONMENTAL IMPACT OF PHOSPHOGYPSUM:
i.
ii.
iii.
iv.
In order to reduce the toxic contents from the phosphogypsum, they are
treated with various solvent extraction process or many different
technologies
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
Phosphoric
Acid,
Hindwai
Publishing
corporation,
ISRN
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ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
ManufacturingofPhosphoricAcidusingRockPhosphateandSulfuricAcid
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