1.

Presentation of the Host Organization

1.1. Presentation of JESA S.A

JESA is the African leader in design, engineering, project delivery,

and asset management, offering its clients superior value through
comprehensive, innovative, and sustainable solutions for industrial
and urban development. JESA is the product of the joint venture
created in 2018 between the Office Chérifien de Phosphate (OCP)
and Worley.

As one of the largest engineering companies in Africa and Morocco,

covering mining, industry, urban development, and infrastructure,
JESA combines the expertise and resources of both parent
companies to provide end-to-end solutions for the phosphate and
fertilizer industry, from exploration and mining to processing and
distribution. It offers services such as feasibility studies,
engineering design, project management, and construction
management.

JESA also focuses on sustainability and aims to promote sustainable

development within the phosphate industry. It seeks to provide
innovative solutions that reduce environmental impact, improve
efficiency, and support the development of local communities.
1.2. Evolution of JESA

JESA's history marks a significant evolution in its national and

continental career. The company's growth over a short period,
amidst intense competition among consulting firms vying for OCP
and Worley as primary clients, represents a challenge that JESA has
successfully met.
1.3. JESA's Services

JESA operates across all engineering sectors and offers a complete

range of services and capabilities in mining and industry, energy,
water, planning and construction, environment, transportation, as
well as infrastructure.

1.4. JESA's Missions, Visions, and Values

The table below summarizes the missions, principles, visions, and

values of JESA S.A.

Categor
Description
y

To be the African leader in design, engineering,

project delivery, and asset management services. To
Missions
provide end-to-end, innovative, and sustainable
solutions for industrial and urban advancement.

Safety: Every one of us makes safety a personal value

Principl that we practice every day. Integrity: Everyone at JESA
es is obligated to protect JESA's reputation and report
any observed unethical behavior.

Bringing solutions with an African touch to global

Visions
issues.
 Profitable growth for all stakeholders; Clients are
Values valued partners; Human resources are the beating
heart of the company.

1.5. Company Fact Sheet

A company fact sheet is a document presenting the main

information about a company.

Information Detail

Company Name JESA

Public Limited Company (Société Anonyme -

Legal Form
SA)

CEO Hicham KABBAJ

Sector of Engineering, coordination, and supervision of

Activity industrial works

Date of
2010
Establishment

Shareholders OCP, WORLEY

 Share Capital 45,000,000 MAD

Turnover 600,000,000 MAD

PARK 1100, Casablanca Nearshore, SHORE 27,

Head Office
Bd Al Qods, Casablanca

Website https://www.jesagroup.com

1.6. Organization Chart

The piping section within JESA falls under the Engineering

department at Casablanca Nearshore. All engineering missions
across JESA's projects, particularly for its clients OCP and Worley,
are executed through this department. The organizational chart
below shows the hierarchical structure of the piping department and
our position within the team. Our internship took place within the
piping department, and the following chart summarizes the
hierarchy directly related to our positions as piping interns at JESA.

(Image Placeholder: Figure 6: Piping Department Organization Chart

- ????????????

A simplified organization chart summarizes the hierarchy we

followed within JESA's piping department, as shown in Figure 7.

(Image Placeholder: Figure 7: Simplified JESA Casablanca

Organization Chart????????????????????????????????????

1.7. Organization

Project-based work requires implementing a specific organization

that overlays the company's structure to adapt to the technical,
scientific, economic, social, and political environment. JESA adopts a
matrix project organization, represented in the table [Figure 8]. A
hierarchy is "functional" and ensures that each type of expert in the
organization is well-trained and evaluated by a manager who is a
super-expert in the same field to manage projects, allowing them to
adopt a cross-functional structure: functional departments and the
project director are jointly responsible for project performance.

1.8. JESA Steps Project Management

1.8.1. Definition of the JSTEP Methodology

Project management involves organizing the progress of a project

from A to Z, from its conception phase to its final phase. To do this,
objectives, necessary human and material resources, budget,
deadlines, and potential constraints must be defined. JESA
distinguishes itself from its competitors through a project
management methodology that undoubtedly helps it accomplish its
missions based on balancing the criteria of cost, quality, and time.
The following table summarizes the steps to follow to apply this
methodology.

Step Objective Description

Define and identify possible directions for a project,

Step
performing an initial motivated analysis, defining a scope,
1
and an initial estimate to ensure its viability.
 Define the best strategy, analyze different conceivable
Step
options, and consolidate the estimate to confirm project
2
viability.

Finalize the process, client objectives, studies, project

Step scope, main equipment price offers, and the project
3 execution plan (PEP) to consolidate the estimate and
obtain project funding.

Direct, coordinate, and finalize studies, purchase

Step
necessary equipment for procurement, construction, and
4
start-up operations.

Mobilize and direct contractors so they carry out

Step
installations according to plans and Issued For
5
Construction (IFC) documents.

Step Direct acceptance and commissioning operations to

6 validate compliance with expected performance.

Close out the project having properly conducted all

Step
required regulatory and contractual activities (including
7
archiving).

(Caption: Table 3: Objectives of the JESA Steps Phases)

The first four steps are executed at JESA's engineering offices:

 Phase 01: Opportunity Analysis - Feasibility Study.

 Phase 02: Conceptual.

 Phase 03: Basic Design.

 Phase 04: Detailed Design/Procurement.

The remaining three phases are executed on-site by JESA teams:

 Phase 05: Construction.

 Phase 06: Start-up.

 Phase 07: Close-out.

1.8.2. Chronological Order of STEPS

Each phase extends over a period; one phase may begin before
another ends. As activities progress through the seven phases,
permanent activities are implemented, namely drafting progress
reports, tracking client satisfaction expectations, conducting quality
audits, monitoring cost and schedule indicators, quantities,
implementing JVEP (JESA Value Engineering Program), Value Plus
initiatives, and capturing lessons learned.

(Image Placeholder: Figure 9: Chronological order of steps)

1.8.3. Deliverables of STEPS

To ensure the effective progress of each JSTEP phase, a deliverable

must be produced that describes the outcome of the phase and
serves to initiate the next phase. After each phase, there is a
milestone review to check all documents from that phase, ensuring
its completion. If a deliverable does not meet the requirements, a
new iteration of the relevant step is performed until it is correctly
addressed.

2. Piping Department at JESA

2.1. Introduction

Piping systems in a chemical plant (refineries, petrochemical plants,

fertilizer plants, gas plants, etc.) are comparable to arteries and
veins through which fluids, vapors, slurries, solids, etc., flow under
various conditions imposed by the plant's process design. The piping
network is subjected to almost all the most severe conditions of the
plant, such as temperature, pressure, flow rate, and combinations
thereof.

In addition to the above, corrosion, erosion, toxic conditions, and

radioactivity add further problems and difficulties to pipe design.
With advancements in process design and technological
development, continuous effort must be pursued to meet process
requirements. This makes the work of a piping engineer more
complex and responsible.

In almost all chemical industries, the installed capital cost of piping

is a major factor in plant investment.1 Regarding material
procurement, excluding equipment costs, piping is the largest
component of plant costs. It is also observed that piping
significantly exceeds all other field costs. Furthermore, design
engineering utilizes approximately 45% of engineering work-hours,
and 50% of these hours are used in piping design.

(Image Placeholder: Figure 10: Distribution of costs related to the

Piping Department)

2.2. Structure of the Piping Department

As mentioned earlier, the piping department consists of three

sections. Table 4 describes each section:

Section Description

Responsible for drafting plans and drawings for

the construction, operation, and layout of piping
Design/
systems. These systems move utility resources like
Layout
water, wastewater, oil, and natural gas. The piping
designer must define a logical and efficient system.

Responsible for designing pipe support

components, developing engineering calculations,
evaluating nozzle loads, collaborating with other
Stress
departments, advising management on
engineering issues, and reviewing vendor
documents.

Responsible for creating project piping classes and

the numerous specifications required to
Materials
manufacture, test, insulate, and paint piping
systems.

(Caption: Table 4: Sections of the Piping Department)

For our internship, we belong to the Materials section, responsible

for all pipe material selections.

2.3. Deliverables Produced by the Piping Department

2.3.1. Plot Plan

A drawing indicating the general location of equipment, structures,

roads, buildings, and access ways.
(Image Placeholder: Figure 11: Example of a Plot Plan)

2.3.2. Equipment Layout

A document showing the arrangement of all equipment satisfying

process requirements, safety regulations, ease of operation,
maintenance, and economy.

(Image Placeholder: Figure 12: Example of an Equipment Layout)

2.3.3. Piping Layout

A document showing the arrangement of the piping network to

transport fluids between equipment in a process plant, meeting all
requirements.

(Image Placeholder: Figure 13: Example of a Piping Layout)

2.3.4. 3D Model

A document providing a preview of what the site will look like,

showing the placement of piping systems, equipment, and
accessories. It represents a 3D implementation of the previously
mentioned documents.

(Image Placeholder: Figure 14: Example of a 3D Model)

2.3.5. Piping Isometrics

A 2D drawing in which piping is represented as if in 3D.

(Image Placeholder: Figure 15: Example of a Piping Isometric)

2.3.6. Piping Material Specification (PMS)

The PMS is a piping engineer's primary reference. It consists of

details on materials, dimensions, end types, schedules/thicknesses,
branch connections, non-destructive testing requirements, and
various codes/standards followed for all piping items. Key piping
components detailed in the PMS include: Pipes, Fittings, Flanges,
Steam Traps/Strainers, Bolts, Gaskets, Valves.

A piping class is a document specifying the type of components—

such as pipe type, schedule, material, flange ratings, branch types,
valve types and trim material, gasket, and any other specific
component requirements—to be used for different fluids under
various operating conditions within a plant. The piping class is
developed considering operating pressure, temperature, and the
corrosive environment. Different material specifications are
separated into distinct "piping classes". The piping class is part of
the overall piping specification.

1. Phosphate Rock

1.1. What is Phosphate Rock?

Phosphate rock is a naturally occurring mineral deposit that is rich

in phosphorus (P), an element essential for plant nutrition and
growth. Its primary commercial applications are in the production of
phosphate fertilizers, phosphoric acid (a key industrial chemical),
and as a supplement in animal feeds.

 Chemical Composition: The dominant phosphate mineral within

phosphate rock is typically apatite. The generalized chemical
formula for apatite is

(F,Cl,OH), indicating it is composed of calcium (Ca), phosphate

(PO4) ions, and variable amounts of fluoride (F), chloride (Cl),
or hydroxyl (OH) ions within its crystal structure.

 Phosphorus Content: The commercial value and grade of

phosphate rock are determined by its phosphorus pentoxide
P₂O₅ equivalent content. This content typically varies 10-40%
P₂O₅ .

1.2. Types of Phosphate Rock Deposits

Geologically, phosphate rock deposits are categorized into two main

types based on their origin:
1.2.1. Sedimentary Phosphate Rock (Accounts for approximately
85% of global production)

 Formation: These deposits were formed over millions of years

through the accumulation and diagenesis of phosphorus-rich
organic matter and mineral precipitates in marine
environments.

 Composition: They primarily consist of carbonate-fluorapatite

(often referred to as francolite) and typically contain
associated impurities such as clays, silica (quartz), carbonates,
and organic matter.

 Geographic Examples: Major sedimentary deposits are

widespread globally. Notably, Morocco and Western Sahara
hold the vast majority of the world's known phosphate rock
reserves, estimated to be over 70% of the global total, making
the region a critical global supplier. Other significant deposits
are found in China, the United States (specifically in Florida,
North Carolina, Idaho, and Utah), the Middle East (Jordan,
Saudi Arabia), and North Africa (Egypt, Tunisia).

 Advantages:

o High global abundance and extensive reserves,

overwhelmingly concentrated in Morocco.

o Deposits are often relatively shallow and laterally

extensive, making them amenable to large-scale, lower-
cost open-pit mining methods, as practiced extensively in
Morocco's phosphate basins (e.g., Khouribga, Gantour).

 Disadvantages:

o Generally contain higher concentrations of impurities

compared to igneous sources. This necessitates
beneficiation (physical or chemical processing) to upgrade
the ore quality to meet specifications for downstream
chemical processing, particularly for phosphoric acid
production.

1.2.2. Igneous Phosphate Rock (Accounts for approximately 15% of

global production)
  Formation: These deposits are associated with magmatic
processes, typically found in alkaline igneous intrusions and
carbonatites. The apatite crystallizes directly from cooling
magma.

 Composition: The primary phosphate mineral is fluorapatite,

usually with a lower concentration of impurities compared to
sedimentary ores.

 Geographic Examples: Significant igneous phosphate deposits

occur in Russia (Kola Peninsula), South Africa (Phalaborwa),
Brazil, and Finland.

 Advantages:

o Higher intrinsic purity, often requiring less extensive

beneficiation.

o Frequently preferred as feedstock for producing higher-

quality phosphoric acid (e.g., "merchant grade" for typical
industrial use or purer "food grade") due to lower
impurity levels.

 Disadvantages:

o Deposits are often harder rock and may occur at greater

depths, frequently requiring more complex and expensive
underground mining techniques.

o While beneficiation may be simpler, the overall mining

and initial processing costs can be higher.

2. Phosphate Rock Extraction Process: Methods and Steps

2.1. Surface Mining (Open-Pit Mining) for Phosphate Rock

Surface mining, predominantly through open-pit methods,

represents the most frequently employed and economically
advantageous technique for extracting phosphate rock deposits
situated near the surface (typically at depths less than 100 meters).
This approach facilitates high extraction volumes using relatively
less complex machinery compared to underground mining
operations.

2.1.1. Open-Pit Mining Process Steps

The open-pit mining process for phosphate rock generally involves

the following sequential steps:

Step 1: Site Preparation & Overburden Removal

 Objective: To access the phosphate ore body by removing the

overlying non-phosphate material, known as overburden.

 Process:

o Land Clearing: Initial removal of surface vegetation,

topsoil, and superficial layers using equipment such as
bulldozers and excavators.

o Overburden Stripping: Systematic removal of the layers

covering the phosphate rock (e.g., sand, clay, limestone).
This is typically accomplished using:

 Draglines (large-capacity bucket excavators suitable

for deep overburden).

 Conventional excavator and truck fleets.

 Bucket-wheel excavators (employed in very large-

scale, continuous mining operations).

 Outcome: The phosphate rock layer (ore zone) is exposed and

prepared for extraction.

Step 2: Drilling & Blasting

 Objective: To fracture and loosen the consolidated phosphate

rock mass, facilitating easier excavation and handling.

 Process:

o Drilling Patterns: Based on geological data and

engineering design, a specific grid pattern is established
for drilling boreholes into the exposed phosphate rock
formation.
 o Blasting: The drilled boreholes are loaded with
appropriate explosives (commonly Ammonium Nitrate
Fuel Oil - ANFO, dynamite, or emulsion explosives).

o Detonation: Controlled detonation of the explosives

fractures the rock mass.

 Key Considerations:

o Blast design is optimized by engineers to maximize rock

fragmentation efficiency while minimizing energy
consumption and costs.

o Blasting patterns and charge weights are carefully

managed to minimize ground vibrations and air blast
effects, ensuring the safety and integrity of nearby
structures and the environment.

o Dust suppression measures, such as water sprays or

misting systems, are implemented during drilling and
blasting to mitigate airborne particulate pollution.

Step 3: Excavation & Haulage

 Objective: To excavate the fractured phosphate rock (ore) from

the pit and transport it to the designated processing area (e.g.,
crusher station or beneficiation plant).

 Process:

o Loading: Large hydraulic or electric mining shovels, or

front-end loaders, are used to scoop up the loosened
phosphate ore.

o Haulage: High-capacity haul trucks (typically ranging from

100 to 400-ton payload capacity) transport the ore from
the loading face out of the pit via haul roads.

o Alternative Transport: In some large, optimized mining

operations, conveyor belt systems may be used in
conjunction with or as an alternative to haul trucks for
more continuous and potentially energy-efficient ore
transport.

 Challenges & Engineering Solutions:

 o Mine Design Optimization: Pit slopes, bench heights, and
haul road layouts are meticulously designed and
maintained to ensure operational safety, geotechnical
stability, and efficient material movement.

o Equipment Selection: Engineering decisions involve

selecting the most appropriate loading and hauling
equipment (e.g., evaluating electric versus diesel-
powered haul trucks based on factors like operational
cost, capital investment, mine life, and sustainability
goals).

o Traffic Management: Sophisticated fleet management

systems, often utilizing GPS technology, are employed to
optimize truck dispatching, minimize queuing times,
prevent traffic congestion within the pit, and enhance
overall safety.

Step 4: Crushing & Primary Processing

 Objective: To reduce the particle size of the extracted run-of-

mine (ROM) phosphate ore to dimensions suitable for handling,
transport, and subsequent beneficiation processes.

 Process:

o Primary Crushing: Large chunks of ROM ore are typically

fed into primary crushers (commonly Jaw or Gyratory
crushers) to achieve an initial size reduction (e.g., down
to approximately 30 cm).

o Secondary Crushing: The output from the primary crusher

may undergo further size reduction in secondary crushers
(such as Cone or Impact crushers) to achieve a finer
product size (e.g., around 2-5 cm).

o Screening & Stockpiling: The crushed ore is often

screened to separate different size fractions. The
appropriately sized material is then transferred, often via
conveyor belts, to stockpiles for temporary storage before
being fed to the beneficiation plant.

 Importance of Crushing:
 o Enhanced Beneficiation Efficiency: Reducing particle size
increases the surface area, which improves the efficiency
of downstream separation processes in the beneficiation
plant.

o Improved Material Handling: Smaller, more uniformly

sized particles are easier and more efficient to transport
(e.g., via conveyors) and handle throughout the
processing circuit.

2.2. Underground Mining of Phosphate Rock

Underground mining methods are employed when phosphate

deposits are located at significant depths (typically exceeding 100
meters) where surface mining becomes economically unviable. While
this approach minimizes surface land disturbance, it necessitates
more sophisticated engineering design and operational techniques
to ensure safety, efficiency, and cost-effectiveness.

The selection of a specific underground mining method is contingent

upon various factors, including the geological characteristics of the
deposit, the stability of the surrounding rock mass (host rock), and
the geometry (shape and orientation) of the ore body. Commonly
utilized methods for phosphate extraction include Room and Pillar
Mining, Longwall Mining, and Cut and Fill Mining.

Regardless of the specific extraction method chosen, underground

phosphate mining typically involves three critical operational
phases:

1. Site Preparation & Access Development (e.g., Shaft Sinking or

Decline Construction)

2. Ore Extraction (Stoping)

3. Material Haulage & Transportation

2.2.1. Site Preparation & Shaft Sinking

 Purpose:

o To establish primary access from the surface to the

underground phosphate deposit.
 o To create essential infrastructure pathways for ore
removal, ventilation airflow, personnel movement, and
utility services (power, water, compressed air).

 Key Methods for Shaft Sinking: The method chosen depends on

factors like depth, ground conditions, and required shaft
diameter.

o 2.2.1.1. Conventional Drill & Blast Method (Most Common)

 Process:

1. Pilot Hole Drilling (Optional but common): A

small-diameter guide hole may be drilled from
the surface to the target depth.

2. Drilling: Full-face or bench drilling patterns are

used to create boreholes in the rock at the
shaft bottom.

3. Blasting: Controlled charges of explosives are

placed in the boreholes and detonated to
fragment the rock.

4. Mucking (Rock Removal): The broken rock

(muck) is removed from the shaft bottom,
typically using mechanical loaders (muckers)
emptying into hoisting skips or buckets.

5. Lining & Reinforcement: As the shaft advances

downwards, the walls are stabilized and lined
for structural integrity using materials like
concrete, steel liners, or shotcrete (sprayed
concrete), often combined with rock bolts and
mesh.

6. Ventilation & Safety Systems Installation:

Concurrent with sinking, initial ventilation
ducting and essential safety systems, such as
emergency escape routes, are established.

 Challenges & Solutions:

 Water Ingress: Encountering groundwater

inflows is common. Solutions include pre-
grouting (injecting sealant into the rock ahead
 of excavation) and implementing robust
pumping systems to manage water levels.

 Rock Instability: Weak or fractured rock zones

require engineered support systems, such as
systematic rock bolting, wire mesh installation,
and reinforced concrete lining, to prevent
collapses.

 Gas Accumulation: Potentially hazardous gases

(e.g., methane) can be encountered. Mitigation
involves implementing comprehensive
ventilation systems to dilute and remove
gases, coupled with continuous gas monitoring
and safety protocols.

o 2.2.1.2. Raise Boring Method (Suitable for Large-Diameter

Ventilation or Service Shafts)

 Process:

1. A small-diameter pilot hole is drilled

downwards from an upper level or the surface
to a lower level access point.

2. A large-diameter cutting head (reaming head or

raise bore head) is attached to the drill string
at the lower level.

3. The head is rotated and pulled upwards,

enlarging the pilot hole to the final shaft
diameter by breaking the rock in tension.
Cuttings fall to the lower level for removal.

4. The completed shaft is typically lined with

concrete or steel sets for long-term stability,
depending on ground conditions and function.

 Advantages:

 Generally faster and considered safer than

conventional drill and blast sinking for suitable
conditions.
  Eliminates the need for personnel to work
inside the shaft during the main excavation
phase.

o 2.2.1.3. Blind Shaft Boring (Using Shaft Boring Machines -

SBM or Shaft TBM) (For Deep Mines or Difficult Ground)

 Process:

 A specialized Tunnel Boring Machine (TBM)

adapted for vertical excavation (Shaft TBM or
SBM) drills downwards from the surface.

 These machines often excavate the rock and

simultaneously install a pre-fabricated shaft
lining (e.g., concrete segments) behind them.

 Advantages:

 Offers precise excavation control and can

provide a high degree of automation.

 Enhances worker safety by minimizing

exposure to unsupported ground.

 Can achieve faster excavation rates,

particularly in competent hard rock formations.

 Disadvantages:

 Involves very high initial capital costs for the

specialized machinery.

 Offers less flexibility compared to conventional

methods and may be less economical for
smaller-scale mines or variable ground
conditions.

2.2.2. Ore Extraction (Stoping)

Once access to the ore body is established via shafts or declines, the
primary extraction of the phosphate ore begins. The specific method
employed depends heavily on the deposit's characteristics.

 Main Mining Methods for Phosphate Ore Extraction:

o 2.2.2.1. Room and Pillar Mining (Most Common, especially

for relatively flat, tabular deposits)
  Process:

1. Development: A network of intersecting

tunnels (entries or drifts) is created within the
ore seam, forming a grid pattern.

2. Extraction (Room Creation): Ore is extracted

from the areas between the tunnels, creating
open spaces known as "rooms" or "stopes".
Drilling and blasting are typically used to break
the phosphate rock within these rooms.

3. Pillar Support: Substantial portions of the ore

body are intentionally left unmined between
the rooms, forming rock pillars. These pillars
act as natural supports for the overlying rock
mass (roof).

4. Mucking & Loading: Broken ore from the rooms

is loaded, commonly using Load-Haul-Dump
vehicles (LHDs), and transported via shuttle
cars or conveyor belts towards the main
haulage system.

 Pillar Design & Safety Considerations:

 The size, shape, and spacing of the pillars are

critical engineering design elements, calculated
based on rock mechanics principles to ensure
long-term roof stability and prevent surface
subsidence.

 In areas with weaker roof conditions,

supplementary ground support measures like
roof bolting (installing long bolts into the roof
strata) and wire mesh application are employed
to reinforce the rock mass.

o 2.2.2.2. Longwall Mining (Suitable for extensive, uniform,

and relatively thick seams, often at greater depths)

 Process:

1. Panel Development: Parallel tunnels (gate

roads) are driven into the ore seam, defining a
 large rectangular block of ore known as a
longwall panel (typically 150-300 meters wide
and several kilometers long).

2. Face Exposure: The ore is extracted along the

entire width of the panel (the "longwall face").

3. Mechanical Cutting: A powerful cutting

machine, known as a shearer, travels back and
forth across the face, cutting slices of the
phosphate ore, which falls onto an armored
face conveyor (AFC).

4. Roof Support: Immediately behind the shearer

and conveyor, a line of hydraulic-powered roof
supports (shields or chocks) temporarily holds
up the roof along the active face.

5. Controlled Caving: As the shearer cuts and the

face advances, the hydraulic supports are
sequentially advanced forward, allowing the
roof behind the supports to collapse in a
controlled manner into the mined-out area (the
"goaf" or "gob").

 Advantages:

 Achieves very high ore recovery rates within

the panel (often 75-90% or higher).

 Allows for highly mechanized, continuous

operation with potentially reduced reliance on
drilling and blasting at the face.

 Challenges:

 Requires significant upfront capital investment

in specialized longwall machinery (shearer,
supports, conveyor).

 Necessitates careful geological assessment and

sophisticated roof control engineering to
manage the stresses and potential for
subsidence. Less flexible in adapting to
 geological variations compared to Room and
Pillar.

2.3. Post-Extraction Treatment of Phosphate Rock & Impurity

Removal

Once phosphate rock is mined (either through surface or

underground methods), it typically undergoes a series of physical
and chemical processing steps known as beneficiation. The goal is to
increase the concentration of the valuable phosphate mineral
(apatite) and remove unwanted impurities (gangue minerals) before
the rock is used in downstream processes like phosphoric acid
production or fertilizer manufacturing.

2.3.1. Beneficiation of Phosphate Rock

 Goal: To increase the P₂O₅ content by removing undesirable

impurities such as silica (sand), clay minerals, carbonates
(limestone, dolomite), iron oxides, organic matter, and
potentially heavy metals.

 Main Steps in Beneficiation: (Note: The specific sequence and

combination of steps vary significantly depending on the ore
characteristics)

o 2.3.1.1. Crushing & Grinding (Comminution)

 Purpose: To reduce the particle size of the mined ore

to liberate the phosphate minerals from the
associated gangue minerals, preparing it for
subsequent separation processes. This is often a
continuation or refinement of the initial crushing
described in Step 4 (Section 2.1.1).

 Process:

1. Primary Crushing: If not already done at the

mine site, large chunks of ROM ore are reduced
using jaw or gyratory crushers.

2. Secondary & Tertiary Crushing: Further size

reduction using equipment like cone crushers
or hammer mills.

3. Grinding: Final stage of size reduction, typically

carried out in wet conditions using ball mills or
 rod mills, to achieve the fine particle size (e.g.,
often around 0.1 mm or finer) required for
effective separation, especially by flotation.

 Key Engineering Considerations:

 Achieving the optimal particle size (grind size)

is crucial; over-grinding wastes energy and can
create slimes that hinder separation, while
under-grinding results in poor liberation and
lower recovery.

 Crushing and grinding circuits are designed to

maximize efficiency and minimize energy
consumption, as comminution is typically the
most energy-intensive part of mineral
processing.

o 2.3.1.2. Washing, Desliming & Screening

 Purpose: To remove very fine particles, primarily

clays (slimes), which can coat valuable minerals,
consume reagents, and interfere with downstream
processes like flotation. Also used to separate the
ore into different size fractions for targeted
processing.

 Process:

1. Washing/Scrubbing: Ore may be vigorously

agitated with water in scrubbers or log washers
to break down clay aggregates and wash away
fine coatings.

2. Screening: Vibrating screens are used to

separate the ore slurry into different particle
size ranges (e.g., coarse, medium, fine).

3. Desliming: Often involves hydrocyclones or

classifiers, which use centrifugal force or
differential settling velocities in water to
separate the ultra-fine slime fraction (< 10-20
microns) from the coarser, valuable mineral
particles.
  Efficiency Factors: Process efficiency depends on
water quality, water pressure, the amount and type
of clay present in the ore, and the efficiency of the
screening and classification equipment.

o 2.3.1.3. Flotation (Most Common Method for Fine Particle

Separation)

 Purpose: To selectively separate fine phosphate

mineral particles from fine gangue particles
(especially silicates and carbonates) based on
differences in their surface chemical properties.

 Process:

1. Conditioning: The ore slurry (pulp) is mixed

with specific chemical reagents in conditioning
tanks. These reagents selectively alter the
surface properties of either the phosphate
minerals or the gangue minerals. Common
reagents include collectors (e.g., fatty acids for
direct flotation of apatite, or amines for reverse
flotation of silica) and modifiers (e.g., pH
regulators like soda ash or caustic soda,
depressants to prevent unwanted minerals
from floating).

2. Flotation Cells: The conditioned pulp flows into

flotation cells where air is injected, creating
fine bubbles.

3. Attachment & Separation: Depending on the

reagents used (direct vs. reverse flotation),
either the phosphate particles or the gangue
particles attach to the air bubbles and rise to
the surface, forming a froth layer. This froth,
enriched in the floated mineral, is skimmed off.
The particles that do not float remain in the
pulp and exit as tailings. Multiple stages of
flotation (rougher, cleaner, scavenger) are
often used to maximize recovery and grade.

 Efficiency Factors: Effective flotation relies heavily

on precise control of reagent types and dosages,
 pulp density, pH level, particle size, and aeration
rate.

 Challenges: Requires careful management and

treatment of process water to remove or recycle
residual chemicals before discharge or reuse. The
effectiveness can be sensitive to variations in ore
mineralogy.

o 2.3.1.4. Magnetic & Electrostatic Separation (Used for

Specific Impurities)

 Purpose: Used less commonly than flotation but can

be effective for removing specific types of impurities
based on differences in magnetic susceptibility or
electrical conductivity.

 Process:

 Magnetic Separation: Primarily used to remove

strongly or weakly magnetic iron-bearing
minerals (e.g., magnetite, hematite, ilmenite)
using various types of magnetic separators
(low-intensity for magnetite, high-intensity for
weaker minerals).

 Electrostatic Separation: Can sometimes be

used to separate minerals based on differences
in their surface charge when passed through an
electric field (e.g., separating conductive
minerals from non-conductive ones).

 Applicability: Often used as an auxiliary process or

for ores with specific characteristics, such as high
iron content where magnetic separation is viable.
Not universally applicable to all phosphate ore
types.

2.3.2. Chemical Treatment for Further Purification

In some cases, particularly depending on the specific impurities

present and the required final product quality, further chemical
treatments may be applied after or in conjunction with beneficiation
steps.
 2.3.2.1. Calcination (Primarily for Carbonate-Rich Phosphate
Rock)

o Purpose: To decompose carbonate minerals (e.g., CaCO₃,

MgCO₃) present as impurities by applying high
temperatures, thereby increasing the relative P₂O₅
content of the rock.

o Process: Beneficiated or raw phosphate rock is heated to

high temperatures (typically around 900-1000°C) in a
large rotating furnace (rotary kiln). The heat causes
thermal decomposition of carbonates (e.g., CaCO₃ → CaO
+ CO₂↑), releasing carbon dioxide gas and leaving a solid
product (calcine) enriched in phosphate.

o Effectiveness: Can significantly increase the P₂O₅ grade

(e.g., potentially from ~30% to ~37%) by removing the
weight associated with CO₂.

o Challenges: Highly energy-intensive due to the high

temperatures required. Can alter the reactivity of the
phosphate rock for subsequent acidulation processes.

 2.3.2.2. Acid Leaching (Selective Dissolution of Impurities)

o Purpose: To selectively dissolve certain metallic

impurities, particularly iron (Fe₂O₃) and aluminum (Al₂O₃)
oxides/hydroxides, using acidic solutions, while
minimizing dissolution of the phosphate mineral.

o Process: Phosphate rock (usually ground) is reacted with

a dilute acid solution (e.g., weak H₂SO₄, HCl, or citric acid)
under controlled conditions. Impurities dissolve into the
liquid phase, which is then separated from the purified
solid phosphate rock via solid-liquid separation (e.g.,
filtration).

o Applicability: Primarily considered for ores with high iron

and aluminum content that negatively impact
downstream processing.

o Environmental Concerns: Requires careful management

and treatment/neutralization of the spent acid solution.
 Process conditions must be optimized to prevent
significant loss of valuable phosphate.

2.3.3. Impurities in Phosphate Rock & Their Impact

Effect on Phosphoric Acid

Element/Compound Designation Type
Production

Consumes H2SO4, forms gypsum

CaO Quicklime Major
(filterability is key).

Phosphorus Desired product source; its

P2O5 Major
pentoxide concentration defines ore grade.

Consumes H2SO4, causes foaming in

CO2 Carbon dioxide Major
reactor.

Causes corrosion (HF, H2SiF6), scaling

F Fluorine Major
(fluosilicates), P2O5 loss.

Reacts with F, can form gels/scales

SiO2 Silica Major
impacting filtration.

Affects gypsum crystal quality, potential

SO3 Sulfur trioxide Major
P2O5 co-precipitation loss.

Causes scaling (Na2SiF6), leading to

Na2O Sodium oxide Major
P2O5 loss.

Magnesium Increases acid viscosity, hinders

MgO Major
oxide filtration, consumes acid.

Increases viscosity, forms sludge/scale

Al2O3 Alumina Major
(Al phosphates/fluorides), P2O5 loss.

Increases viscosity, forms sludge/scale

Hematite
Fe2O3 Major (Fe phosphates), P2O5 loss, colors
(Iron(III) Oxide)
acid.

Causes scaling (K2SiF6), leading to P2

K2O Potassium oxide Major
O5 loss.

Causes severe corrosion (especially to

Chlore Total chlorine Major
stainless steel).

Causes foaming, darkens acid, hinders

C.org Organic Carbon Trace
filtration.

Generally minor process impact; acts

Rare earths
Tr Trace as impurity in final acid (or potential
(REE)
byproduct).
 Impurity in final acid; may limit
Zn Zinc Trace
downstream uses (e.g., feed grade).

Impurity in final acid; can impart color,

V Vanadium Trace
potential byproduct.

Impurity, potential toxicity (Cr VI), colors

Cr Chromium Trace
acid, environmental concern.

Impurity, radioactivity concerns

U Uranium Trace (acid/gypsum), potential valuable
byproduct.

Impurity in final acid; generally minor

Cu Copper Trace
process impact.

Toxic heavy metal impurity; major

Cd Cadmium Trace environmental/health concern,
regulated.

Toxic impurity; environmental/health

As Arsenic Trace
concern.

Impurity; radioactivity concerns

Th Thorium Trace
(acid/gypsum).

Cl soluble Soluble chlorine Trace Causes severe corrosion.

Okay, here is the complete text merged together, incorporating all

the sections and additions, formatted for a Word document:

2.3.3 Impurities in Phosphate Rock & Their Impact

2.3.3.1 Sources and General Effects of Impurities

 Primary Source: Phosphate rock (PR) is the principal source of

dissolved and suspended impurities in wet process phosphoric
acid (WPA).

 Other Sources:

o Process water, particularly brackish water, can introduce

impurities like Chloride (Cl−).

o Contaminated sulfuric acid (H2SO4), sometimes sourced

from the hydrometallurgy industry, can add further
impurities.
  General Effects:

o Impurities impart undesired color and turbidity to WPA.

o They increase the corrosiveness of the acid.

o Some impurities affect the density and viscosity of the

acid, leading to the formation of acid sludge and
sediments.

o Sediments in contact with metallic surfaces can form

deposits that promote localized corrosion.

 Corrosivity:

o Chloride (Cl−) and Fluoride (F−) are particularly corrosive

impurities.

o Other impurities affecting corrosion include SiO2, Al2O3,

alkali metal salts, Sulfate (SO42−), Sulfur (S), organic
matter, and oxidizing agents.

o The corrosivity of an impurity depends on its chemical

nature, concentration, interaction with other acid
constituents, and the specific metal surface.

2.3.3.2 Chloride (Cl−) Impurities

 2.3.3.2.1 Sources of Chloride:

o Phosphate Ore: Cl− typically originates from phosphate

ores, where it exists as alkali metal chlorides (e.g., NaCl).
Washing PR with fresh water can remove some Cl−.

o Process Water: Seawater used for washing PR or in rising

tanks/cargo holds can significantly increase Cl− content.

o Apatite Structure: Chloride may be present within the

apatite itself, sometimes as water-insoluble salts or as
oxychlorides formed during PR calcination.

o Handling and Storage Contamination: Cross-

contamination can occur in fertilizer plants where PR and
muriate of potash (MOP - potassium chloride) are handled
by the same equipment (elevators, conveyors) and stored
in the same building. Residual MOP can mix with the PR.
  2.3.3.2.2 Influence of Chloride Ion (Corrosion):

o Chemical Reactivity: The corrosivity of halide ions (Cl−

and F−) in strong mineral acids (H3PO4, H2SO4) is related
to the high chemical reactivity derived from the
physicochemical properties of halogens
(electronegativity, ion size, ionic character).

o Mechanism:

 Cl− ions adsorb onto metal surfaces, displacing

adsorbed oxygen or water molecules.

 This adsorption shifts the metal's potential to more

active (electronegative) values.

 It causes the breakdown of the passive state,

particularly at elevated temperatures, leading to
pitting corrosion.

o Reaction Products: During the attack on stainless steel

(SS), soluble chlorides of iron, nickel, and chromium are
formed. Their high solubility in PA is aided by the acid's
complexing ability with transition metal cations [14].

o Concentration Effect: Electrochemical parameters

indicating corrosion activity (e.g., icorr) increase as the
Cl− concentration increases.

2.3.3.3 Fluoride (F−) Impurities

 2.3.3.3.1 Formation of Fluoride Species:

o The calcium fluoride (CaF2) component of fluoroapatite in

PR reacts with H2SO4 during acidulation, producing
hydrofluoric acid (HF).

o Depending on the hydrogen ion activity of the solution,

HF exists in equilibrium with its dimer ((HF)2), the
hydrofluoride ion (HF2−), and the fluoride ion (F−),
according to the following equilibria:

(HF)2⇌2HF⇌HF2−+H+⇌2F−+2H+

(HF dimer ⇌ Free HF ⇌ Hydrofluoride ion + Hydrogen ion ⇌ Fluoride

ion + Hydrogen ion)
 2.3.3.3.2 Influence of Fluoride and Mitigation:

o Fluoride can form complexes like aluminum fluoride ((AlF6

)3−).

o Corrosion Mitigation Reactions: Certain reactions can

decrease corrosion by forming less corrosive species:

 Formation of partially soluble metal fluoride

complexes with ions like Fe3+, Mg2+, Ca2+, and
Na+.

 Formation of insoluble fluoroaluminates and

fluorosilicates that can settle on metallic surfaces.
Examples include:

 Na2SiF6

 NaKSiF6

 MgNaAlF6

 Na3AlF6

 MgSiF6

o Primary Corrosion Agent: The free fluoride ion (F−), which

is not complexed by cations, is considered the main
corrosion agent.

o Role of Silica: Reactive silica (SiO2) decreases the

concentration of free HF by reacting to form silicon
tetrafluoride (SiF4) or hexafluorosilicic acid (H2SiF6).

o Mitigation Strategy: If the reactive silica content in the PR

is low relative to the fluoride content, corrosion can be
decreased by:

 Adding reactive silica during the acidulation stage.

 Mixing the low-silica PR with another PR that has a

high content of reactive silica or aluminum
compounds.

o Experimental Evidence: Laboratory corrosion tests using

30% P2O5 (phosphoric acid) have demonstrated these
effects:
  Tests involved adding HF or complex fluorine
compounds like H2SiF6.

 Weight loss measurements and electrochemical

techniques were used.

 The electrode potential of UNS S31600 stainless

steel shifted to a more active value (from -0.16 V to -
0.23 V) in the presence of HF, indicating an
increased tendency for corrosion.

 Anodic polarization plots revealed anodic dissolution

when HF was added, but stable passive behavior in
the presence of H2SiF6.

2.3.3.4 Cadmium (Cd) Impurities

 Source: Cadmium (Cd) is a toxic heavy metal naturally present

in phosphate rock (PR) deposits, with concentrations varying
significantly depending on the geological origin (sedimentary
rocks often contain more Cd than igneous rocks).

 Significance and Impact:

o Cd is non-essential for plants and is toxic to humans,

animals, and plants above certain threshold levels.

o Long-term application of phosphate fertilizers derived

from high-Cd PR can lead to the accumulation of Cd in
agricultural soils.

o From the soil, Cd can be absorbed by crops, entering the

human food chain and posing health risks (e.g., related to
kidney function and bone health).

 Behavior in WPA Production: During the wet process

phosphoric acid production, a large fraction of the Cd present
in the PR dissolves and follows the phosphorus into the
phosphoric acid product. Consequently, it ends up in the final
phosphate fertilizer products.

 Regulatory Context and Mitigation:

o Due to environmental and health concerns, many regions

(like the European Union) have established regulatory
 limits for the maximum allowable Cd concentration in
phosphate fertilizers.

o Strategies to manage Cd levels include sourcing low-Cd

phosphate rock and employing "decadmiation"
technologies (e.g., solvent extraction, ion exchange,
precipitation) to remove Cd during phosphoric acid
production, although these add complexity and cost.

Okay, here is the text about the definition and chemical properties
of phosphoric acid, adapted to the same structure and formatting
style used previously:

3. Definition and Chemical Properties

3.1 Definition

 Phosphoric acid (H3PO4) is a triprotic acid, meaning it can

release up to three hydrogen ions (H+) in solution.

 It is considered a weak acid compared to strong acids like

sulfuric acid (H2SO4) or hydrochloric acid (HCl).

 Despite being a weak acid, it plays a crucial role in various

industrial and biological processes.

 Key Properties:

o Molecular formula: H3PO4

o Molar mass: 97.99 g/mol

o Appearance: Colorless, odorless, and syrupy liquid in its

concentrated form.

o Solubility: Highly soluble in water, forming an acidic

solution.

3.2 Chemical Structure

 Phosphoric acid consists of one phosphorus (P) atom, four

oxygen (O) atoms, and three hydrogen (H) atoms.

 Its structure features a central phosphorus atom double-

bonded to one oxygen atom and single-bonded to three
hydroxyl (-OH) groups.
  The molecular structure (orthophosphoric acid) arranges these
groups tetrahedrally with the phosphorus atom at the center.

 In aqueous solutions, phosphate ions are considered

interconnected by hydrogen bonds.

 As the solution is diluted, hydrogen bonding between

phosphate ions decreases and is replaced by hydrogen bonding
to water molecules.

3.3 Chemical Properties and Reactivity

 Reaction with Metals:

o Phosphoric acid reacts with reactive metals (e.g., Zinc

(Zn), Magnesium (Mg), Iron (Fe)) to form phosphate
coatings on the metal surface and release hydrogen gas
(H2).

4.Specifications

Technical Grades
Physical Properties

Approximate pH of Phosphoric Acid (H₃PO₄) Solutions at 25°C

Phosphoric acid is a weak triprotic acid, meaning it releases protons

(H⁺) in three steps, each with its own dissociation constant (pKa).
The first dissociation (pKa₁ ≈ 2.15) is the most significant
contributor to the acidity, especially at higher concentrations. The
pH is therefore highly dependent on the acid concentration.
 Concentration (Molarity, Approximate
mol/L) pH

10 M (~67% w/w) ~0.6

5 M (~45% w/w) ~0.8

1 M (~10% w/w) ~1.1

0.5 M (~5% w/w) ~1.4

0.1 M (~1% w/w) ~1.6

0.01 M ~2.2

0.001 M ~3.0

0.0001 M ~3.8

Notes:

 These pH values are approximate and can vary slightly

depending on temperature and the presence of other dissolved
species.

 The relationship between concentration and pH is logarithmic,

not linear.

 The % w/w values are also approximate, as the density of

phosphoric acid solutions changes with concentration.

 At very low concentrations, the second dissociation step (pKa₂

≈ 7.20) starts to have a minor influence on the pH. The third
dissociation (pKa₃ ≈ 12.35) only becomes relevant in neutral to
alkaline conditions.

 These values assume pure phosphoric acid in water. Impurities

present in commercial or wet-process phosphoric acid can
affect the actual pH.
5.BASIC PROPERTIES

5.1.Boiling Points

The boiling point for orthophosphoric acid is shown in Figure which

graphs the boiling point at one atmosphere pres- sure versus the
concentration expressed as weight percent phosphoric acid (% H3
PO4 ). Through the concentration range of 0% to 100%, boiling acid
will give off very nearly pure water.

5.2.Freezing point

The following Figure is the phase diagram of the H3 PO4 -H2 O

system showing the freezing point curve for phosphoric acid through
the range of 0 to 100 weight percent H3 PO4 . Concentrated
phosphoric acid tends to supercool before crystallization occurs. The
freezing points of standard concentra-
tions are as follows:
5.3.Conversion Factors

Phosphoric acid concentrations can be expressed in several ways:

percent phosphoric acid (%H3 PO4 ), percent phosphorous pentoxide
(%P2 O5 ), or percent phosphorus (%P). The following chart gives
the factors to convert from one of the above concentration units to
another.

For example, to convert from 75% H3 PO4 to % P2 O5 : 75% H3 PO4 x 0.724

= 54.3% P2 O5

5.4. Specific heat

the weight percent of phosphoric acid in an aqueous solution versus the

specific heat expressed as calories per gram:
5.5. Density

 The density (often expressed as specific gravity) of

orthophosphoric acid (H3PO4) solutions is directly related to its
concentration. Data illustrating this relationship is available.

 Measuring specific gravity serves as an accurate method for

determining the concentration of phosphoric acid solutions,
particularly for laboratory analysis.

 By using linear interpolation between known data points

relating specific gravity and concentration, the acid
concentration can be determined with an accuracy of
approximately ± 0.05% H3PO4.
6. Health and Safety Information

 Stability: Phosphoric acid is considered a stable chemical, not

typically subject to thermal or photochemical decomposition.

 Polymerization: Hazardous polymerization will not occur.

 Hazardous Decomposition: At high temperatures

(approximately 3000°F to 3200°F or 1650°C to 1760°C),
hazardous decomposition products, specifically phosphorus
oxides (PxOy), are evolved.

 Reactivity with Metals:

o Reacts with some metals, such as aluminum (Al) and zinc

(Zn), liberating hydrogen gas (H2).

o The reaction is generally not as rapid or violent compared

to more active acids.

o Caution: The byproduct hydrogen (H2) is very flammable

and requires caution.

6.1 Fire and Explosion Hazard

 Flammability: Phosphoric acid itself does not burn.

 Explosion Risk: It exhibits no unusual fire or explosion hazards.

 Exposure Limit: The Threshold Limit Value Time Weighted

Average (TLV-TWA) is 1.00 milligram per cubic meter of air
(mg/m3).

 Inhalation: Excessive breathing of mists or vapors can cause

respiratory irritation.

 Contact Irritation: Can cause moderate eye irritation and slight

skin irritation at lower concentrations or brief exposures.
6.2 Toxicological Information

 Oral Toxicity: Exhibits slight oral toxicity in rats, with an LD50

(Lethal Dose, 50%) of 1530 mg/kg of body weight.

 Dermal Toxicity: Dermal toxicity is considered slight, based on

testing of similar products and/or its components.

 Skin Contact: Can cause severe skin irritation or burns upon

prolonged or concentrated contact.

 Eye Contact: Will cause eye burns.

 Detailed Data: Detailed toxicological information is available

from PCS Environmental Services Department, Northbrook, IL.

Okay, here is the text about the Wet Process for phosphoric acid
production, formatted in the established report structure:

7. Phosphoric Acid Production: The Wet Process

7.1 The Wet Process: Production Steps

7.1.1 Reaction Step: Acidulation of Phosphate Rock

 The wet process commences with the acidulation stage. Finely

ground phosphate rock is mixed with sulfuric acid (H2SO4) in a
reactor vessel.

 Key Chemical Reaction:

o The primary phosphate mineral in the rock (represented

here as fluoroapatite, Ca5(PO4)3F) reacts with sulfuric
acid (H2SO4).

o The main products are phosphoric acid (H3PO4) and

calcium sulfate dihydrate (CaSO4⋅2H2O), commonly
known as gypsum. Gypsum is largely insoluble under
reaction conditions and must be separated later.

o Hydrofluoric acid (HF) is also generated due to the typical

fluoride content of the phosphate rock.
7.1.2 Control of Sulfuric Acid Concentration

 Maintaining the concentration of the feed sulfuric acid (H2SO4)

typically within the range of 93–98% is crucial for several
reasons:

1. Reaction Rate: Higher sulfuric acid concentration

generally accelerates the acidulation reaction rate.

2. Crystallization of Gypsum: Proper acid concentration

control is vital for forming gypsum crystals with good
filterability characteristics, which improves the efficiency
of the subsequent separation step.

3. Energy Efficiency: Producing a stronger initial phosphoric

acid concentration reduces the energy required for water
removal in later evaporation stages.

7.1.3 Filtration: Separation of Gypsum and Acid

 Following the reaction stage, the resulting slurry (mixture of

phosphoric acid solution and solid gypsum) is directed to a

⋅2H2O) from the liquid phosphoric acid.

filtration system. This step separates the solid gypsum (CaSO4

 Filtration Process:

o Solid-Liquid Separation: Gypsum solids are separated

from the acid using techniques such as vacuum filtration
or pressure filtration.

o Washing: The separated solid filter cake (gypsum) is

washed, typically with water, to recover phosphoric acid
that would otherwise be lost with the cake.

o First Acid Output: The liquid filtrate obtained from this

stage is crude wet-process phosphoric acid, typically
containing about 28-32% phosphorus pentoxide (P2O5),
which corresponds to approximately 40-50% H3PO4 by
weight.

7.1.4 Evaporation: Acid Concentration Enhancement

 The phosphoric acid produced after filtration is often too dilute

for direct use or sale and requires concentration. This is
 achieved through evaporation to increase the phosphorus
pentoxide (P2O5) content.

 Concentration Stages:

o Commercial/Fertilizer Grade: In a common first

evaporation stage, the acid is concentrated to about 48-
54% P2O5 (approximately 66-75% H3PO4). This
concentration is suitable for producing many phosphate
fertilizers and for some commercial applications.

o Further Purification & Concentration: For higher purity

grades required in applications like food,
pharmaceuticals, or cosmetics, the acid undergoes
additional purification steps (e.g., solvent extraction, ion
exchange, precipitation, adsorption) often followed by
further concentration, sometimes reaching higher
strengths like "superphosphoric acid".
7. Phosphoric Acid Production: Thermal Process

7.1 Thermal Process: Production Steps

7.1.1 Raw Materials and Initial Preparation

 The thermal process typically starts with elemental phosphorus

(often in the form of P4).

 This elemental phosphorus is first produced by the reduction of

phosphate rock in an electric arc furnace at high temperatures,
using coke (carbon, C) as a reducing agent and silica (SiO2) as
a flux.

 Phosphorus Production Reaction:

o Phosphate rock (represented as Ca3(PO4)2) reacts with

silica (SiO2) and carbon (C).

o The products are calcium silicate (CaSiO3) slag, carbon

monoxide (CO) gas, and elemental phosphorus (P4) vapor.

o The phosphorus (P4) vapor is distilled off and condensed

(typically under water) for collection.

7.1.2 Combustion of Phosphorus

 The collected elemental phosphorus (P4) is then burned in a

controlled supply of dry air or oxygen within a dedicated
combustion chamber.

 This combustion occurs at very high temperatures

(approximately 1800–3000°C).

 The primary product of this combustion is phosphorus

pentoxide (P2O5), a white solid powder:

o P4+5O2→P4O10 (often written as 2P2O5)

 Careful control of the combustion process is necessary to

ensure complete oxidation and prevent the formation of
unwanted lower oxides of phosphorus or other side reactions.

7.1.3 Hydration and Acid Formation

 The phosphorus pentoxide (P2O5) gas/fume produced during

combustion is then reacted with water (H2O) or dilute
phosphoric acid solution to form phosphoric acid (H3PO4).
  This hydration step typically takes place in specially designed
hydration towers or absorption units:

o P4O10+6H2O→4H3PO4

 The heat generated during hydration must be managed

effectively.

7.1.4 Demisting

 The final step involves removing any fine mist of phosphoric

acid (H3PO4) droplets suspended in the exit gas stream from
the hydration/absorption unit.

 This "demisting" is crucial to prevent product loss and air

pollution.

 It is commonly accomplished using high-efficiency mist

eliminators, such as high-pressure drop demistors or
electrostatic precipitators.
8. Byproducts and Impurities Generated During Phosphoric Acid
Production

Phosphoric acid (H3PO4) is primarily produced through two main

processes: the wet process and the thermal process. Each generates
different byproducts and associated impurities, with the wet process
being particularly known for the large volumes of byproducts
generated.

8.1 Major Byproducts (Primarily from Wet Process)

8.1.1 Phosphogypsum (CaSO4⋅2H2O)

Phosphogypsum is generated in massive quantities during wet-

process phosphoric acid production, estimated at about 5 tons for
every ton of phosphoric acid produced. It is predominantly managed
as a waste product rather than utilized as a valuable byproduct.

Its status as a waste product stems from several factors:

 Radioactivity concerns: Phosphogypsum contains Naturally

Occurring Radioactive Materials (NORM), particularly Radium-
226 (226Ra), derived from uranium naturally present in the
phosphate rock feed. Consequently, regulatory restrictions in
many regions, including the United States, severely limit its
use due to radioactivity levels.

 Contaminants: Besides radioactive elements, phosphogypsum

may contain trace amounts of heavy metals, fluorides, and
other impurities originating from the phosphate rock.

 Limited commercial value: The potential market for

phosphogypsum is very small compared to the enormous
quantities produced annually.

The most common management approach for phosphogypsum is

disposal in large, engineered impoundments known as "gypsum
stacks." These stacks involve pumping phosphogypsum slurry to
designated outdoor storage areas, which can eventually cover
hundreds of acres and reach heights of up to 200 feet, requiring
significant land use and long-term management. Effective water
management systems are crucial for these stacks to control acidic
process water and prevent potential groundwater contamination.

8.1.2 Hydrogen Fluoride (HF) and Related Fluorine Compounds

Hydrogen fluoride (HF) and related fluorine compounds represent

another significant byproduct stream from the wet process requiring
careful management. Unlike the solid waste challenge posed by
phosphogypsum, these fluorine compounds present issues related to
air emissions, water contamination, and corrosion.

Formation: Fluorine compounds are generated when fluoride-

containing minerals in the phosphate rock, typically fluorapatite
(Ca5(PO4)3F), react with sulfuric acid during the acidulation step.
This reaction initially releases fluoride often as silicon tetrafluoride
(SiF4) gas. This SiF4 gas subsequently reacts with water (either
present in the process or in scrubbing systems) to form aqueous
solutions containing hydrofluoric acid (HF) and fluorosilicic acid (H2
SiF6).

Okay, here is the continuation of the text on byproducts and

impurities, formatted using the established structure and balancing
paragraphs with bullet points:

8.1.2.1 Hazards and Concerns

The fluorine compounds generated, particularly hydrogen fluoride

(HF), pose several significant hazards:

 Highly toxic and corrosive: HF is extremely hazardous to

human health, capable of causing severe chemical burns upon
contact and potentially leading to systemic toxicity even
through skin absorption.

 Environmental impact: Uncontrolled release of fluoride

compounds into the atmosphere can damage vegetation and
negatively impact local air quality. Fluorides in wastewater also
require treatment.

 Equipment damage: Gaseous and aqueous HF are highly

corrosive to many materials, necessitating the use of
 specialized, corrosion-resistant materials in process equipment
handling these streams.

8.1.2.2 Management Approaches

Effective management strategies are employed to control fluoride

emissions and handle these byproducts:

 Emission control systems: Process off-gases containing fluoride

compounds are treated, typically using:

o Wet scrubbers (e.g., absorption towers, venturi

scrubbers) designed for high-efficiency removal and
capture of fluorides from gas streams.

 Recovery as byproducts: Captured fluoride values can be

converted into marketable products, including:

o Fluorosilicic acid (H2SiF6), which is commonly sold for use

in water fluoridation.

o Aluminum fluoride (AlF3), used in the aluminum

production industry.

o Synthetic cryolite (Na3AlF6), another material used in

aluminum smelting.

 Regulatory compliance: Facilities operate under strict

environmental regulations that impose limits on fluoride
emissions, often requiring continuous monitoring systems to
ensure compliance.

8.1.3 Silicon Tetrafluoride (SiF4)

Silicon tetrafluoride (SiF4) is a gaseous intermediate byproduct

formed during the initial reaction of fluoride minerals with sulfuric
acid in the presence of silica. As mentioned previously, it is typically
captured in scrubbing systems where it reacts with water, largely
converting into fluorosilicic acid (H2SiF6).

8.2 Impurities in Wet Process Phosphoric Acid

Beyond the major byproducts, the crude phosphoric acid produced

via the wet process contains various impurities derived primarily
from the phosphate rock feedstock. These impurities can influence
acid quality, downstream processing, and final product
specifications.
8.2.1 Heavy Metals

Several heavy metals can be present as trace impurities:

 Cadmium (Cd)

 Lead (Pb)

 Arsenic (As)

 Mercury (Hg)

 Chromium (Cr)

These metals originate from the phosphate rock and tend to dissolve
and concentrate to varying degrees in the phosphoric acid during
the wet process. Their presence, particularly Cadmium, is a
significant concern for fertilizer quality and food chain accumulation.

8.2.2 Radioactive Elements

Naturally occurring radioactive elements found in phosphate rock

deposits also partially transfer to the acid:

 Uranium (U)

 Thorium (Th)

 Radium (Ra) (and its decay products)

While most of the radium co-precipitates with phosphogypsum,

uranium and thorium tend to follow the phosphoric acid.

8.2.3 Other Impurities

Other common impurities include:

 Iron (Fe)

 Aluminum (Al)

 Magnesium (Mg)

 Sodium (Na)

 Potassium (K)

 Sulfate (SO42−) (residual from sulfuric acid)

 Silica (SiO2) (unreacted or dissolved)

 Organic matter
These impurities can affect the acid's physical properties (color,
viscosity), contribute to scaling or sludge formation during storage
or concentration, and influence its suitability for different
downstream applications, often requiring specific purification steps
depending on the final intended use.

9. Purification Techniques

Phosphoric acid produced from phosphate rock (wet process) or

elemental phosphorus (thermal process) often requires purification
to meet specifications for various applications. Purification aims to
remove impurities such as fluorides, sulfates, heavy metals (like
cadmium, arsenic), suspended solids, color bodies, organic
contaminants, and excess metallic ions (like iron, aluminum,
magnesium, calcium). The primary purification methods include:

9.1 Solvent Extraction-Based Processes

Liquid–liquid extraction is a widely used purification method that

separates phosphoric acid from water and many impurities using
selective organic solvents.

 Common Solvents Used:

o Methyl Isobutyl Ketone (MIBK)

o Tributyl Phosphate (TBP)

o Amine-based solvents

o Alcohols (e.g., Cyclohexanol, n-Octanol)

 Process Description:

o Impure wet-process phosphoric acid (WPA) is intimately

mixed with an immiscible or partially miscible organic
solvent.
 o The solvent selectively extracts the phosphoric acid (H3
PO4), leaving many impurities (especially ionic salts)
behind in the aqueous raffinate phase.

o The loaded solvent (containing H3PO4) is then separated

from the raffinate.

o Finally, the phosphoric acid is recovered (stripped) from

the solvent, often by contacting it with water, yielding a
purified acid solution.

 Effectiveness: This method is generally efficient for removing

significant amounts of sulfate, calcium, iron, aluminum,
magnesium, and other metallic impurities.

9.2 Crystallization & Cooling (Cold Acid Purification - CAP)

Crystallization offers an alternative purification route, particularly

for achieving high purity levels. It operates by cooling concentrated
phosphoric acid to selectively crystallize H3PO4 hemihydrate (H3
PO4⋅0.5H2O), leaving impurities concentrated in the remaining liquid
mother liquor.

Fractional crystallization techniques are employed, often using

static crystallizers for the highest purities needed in applications
like semiconductor manufacturing. In a typical static crystallizer,
vertical plates suspended in the molten feed are cooled by a
circulating heat transfer medium. This causes a layer of pure H3PO4
hemihydrate crystals to grow on the plates, rejecting impurities into
the surrounding melt. Once the desired amount of crystal growth is
achieved, the impure mother liquor is drained. Subsequently, the
plates are gently heated to melt the pure crystalline layer, and the
purified phosphoric acid is collected. The crystallizer is then refilled
for the next cycle.

 Advantages:

o Can achieve very high purification efficiency, especially

for removing sulfates and certain metallic cations that co-
crystallize poorly.

o Avoids the use of organic solvents, potentially reducing

environmental concerns and costs associated with solvent
recovery and losses.
  Disadvantages:

o Can be energy-intensive due to the cooling (refrigeration)

and subsequent remelting steps.

o May be less effective than solvent extraction for removing

certain heavy metals or specific ionic impurities,
depending on their behavior during crystallization.

9.3 Membrane Separation

Membrane-based separation techniques utilize semi-permeable

membranes to selectively separate components from the phosphoric
acid solution based on factors like particle size, ion charge, and
molecular weight. Different membrane types target different
impurities.

9.3.1 Ultrafiltration (UF)

 Purpose: Primarily used to remove colloidal particles,

suspended solids, organic matter, and high molecular weight
compounds (e.g., silica complexes).

 Process: WPA is passed across an ultrafiltration membrane

(pore sizes typically 0.01 to 0.1 microns). Larger particulate
and colloidal impurities are retained by the membrane
(retentate), while the phosphoric acid solution containing
dissolved ions passes through as permeate.

9.3.2 Nanofiltration (NF)

 Purpose: Targets the separation of dissolved multivalent ions

(like Ca2+, Mg2+, Fe3+, Al3+, and SO42−) while allowing
phosphoric acid and monovalent ions to pass through.

 Process: Uses membranes with smaller pore sizes (around 1-10

nanometers) than UF. Under pressure, the membrane rejects
most multivalent ions, concentrating them in the retentate
stream, while allowing a significant portion of the H3PO4 and
monovalent ions (like Cl−, Na+) to pass into the permeate.

9.3.3 Reverse Osmosis (RO) – Final Polishing for High Purity

 Purpose: Employed typically as a final polishing step to achieve

ultra-pure phosphoric acid, removing residual dissolved salts
(both monovalent and divalent ions) and trace contaminants.
  Process: Operates at higher pressures (e.g., 30-80 bar)
compared to NF/UF, using dense membranes that are highly
restrictive to dissolved solutes. Water and potentially some H3
PO4 are forced through the membrane, leaving behind almost
all ionic and organic impurities. This process is capable of
producing electronic-grade or food-grade phosphoric acid from
already partially purified feed.

Okay, here is the section on Chemical Precipitation formatted using

a mix of paragraphs and bullet points for structure and clarity,
similar to the earlier sections on other purification techniques:

9.4 Chemical Precipitation

Chemical precipitation is a purification technique used to remove

dissolved impurities from phosphoric acid by adding specific
chemical reagents. These reagents react with the target impurities
to form insoluble solid compounds (precipitates), which can then be
physically separated from the acid, typically through filtration or
sedimentation. This method can target a range of impurities
common in wet-process phosphoric acid.

 Common Precipitating Agents and Targets:

o Lime (CaO) or Limestone (CaCO3): Primarily used for bulk

removal of sulfate ions (SO42−) by precipitating them as
calcium sulfate (CaSO4). Also used for pH adjustment.

o Sodium Carbonate (Na2CO3), Calcium Hydroxide (Ca(OH)2

), or Sodium Hydroxide (NaOH): Used to raise pH,
precipitating metals like Iron (Fe3+) and Aluminum (Al3+)
as hydroxides (e.g., Fe(OH)3) or carbonates.

o Sulfide Reagents (e.g., NaHS, H2S, Na2S): Effective for

precipitating specific heavy metals such as Arsenic (As),
Cadmium (Cd), Lead (Pb), Mercury (Hg), and Copper (Cu)
as highly insoluble sulfides. Requires careful handling and
pH control due to toxicity.

o Ammonia (NH3) or Ammonium Compounds: Can

precipitate complex ammonium metal phosphates
 (involving Fe, Al, Mg) and certain fluorine compounds,
sometimes used with alcohols.

o Sodium Salts (e.g., Na2CO3, NaOH): Can aid in

precipitating fluorine and silica as complex sodium
fluorosilicates or fluoroaluminates.

The effectiveness of chemical precipitation depends heavily on

controlling process conditions like pH, temperature, reagent dosage,
mixing intensity, and reaction time for optimal precipitation
efficiency. Following the reaction, efficient solid-liquid separation
(e.g., filtration, clarification) is essential to remove the generated
sludge containing the impurities.

 Advantages:

o Relatively simple and well-established technology.

o Can be cost-effective, especially using inexpensive

reagents like lime.

o Effective for removing specific bulk impurities (like

sulfates) or targeted toxic metals (like Arsenic via
sulfidation).

 Disadvantages:

o Generates significant quantities of solid sludge requiring

handling and disposal.

o Risk of co-precipitating valuable phosphate (P2O5),

leading to yield losses if conditions are not optimal.

o May introduce other ions into the acid (e.g., Na+ from
sodium-based reagents).

o Operating costs can increase due to chemical

consumption.

o Requires careful control over process variables (especially

pH).

o Handling toxic reagents like sulfides poses safety and

environmental challenges.

Chemical precipitation is frequently used as a pre-treatment step for

crude wet-process phosphoric acid, particularly to reduce high
sulfate levels or remove specific metallic contaminants before
further purification stages. It is common in the production of
fertilizer-grade acid to improve clarity and quality.

Impurities Efficienc
Method Application
Removed y

Fluoride, sulfates, Moderat

Precipitation Fertilizer-grade
heavy metals e

Food &
Solvent Heavy metals,
High electronic-
Extraction fluoride
grade

Membrane Colloids, sulfates, High-purity

High
Separation metals acid

Crystallization Calcium, sulfates, Moderat

Industrial use
(CAP) fluoride e

10. Storage of Phosphoric Acid

The storage of phosphoric acid at the Jorf Lasfar processing plant

presents specific challenges, significantly influenced by its coastal
location. Proximity to the Atlantic Ocean introduces high humidity
and salt-laden air, creating a more aggressive corrosive external
environment compared to inland facilities. This interacts with the
inherent corrosivity of the stored acid itself.
When phosphoric acid remains static within storage tanks at this
location, several corrosion mechanisms become particularly
concerning:

 Stagnation Corrosion: Lack of fluid movement allows sediments

(impurities or precipitates) to accumulate at the tank bottom
and permits acid stratification. This can create localized
corrosion zones where varying acid concentrations, impurity
levels, or pH differences accelerate metal loss, especially under
deposits.

 Atmospheric Corrosion Interaction (Uniform Corrosion):

Storage tanks face a dual challenge: internal corrosion from
the phosphoric acid and external corrosion from the humid,
salty coastal atmosphere. This combined attack can accelerate
deterioration, particularly at potential weak points like vents,
roof seams, inspection hatches, nozzles, and external
instrumentation connections.

 Pitting Corrosion: Concentrated phosphoric acid is known to

cause pitting corrosion, forming isolated, deep pits that can
eventually penetrate the tank walls. This form of attack often
initiates under sediment deposits, at coating defects, or in
areas where protective linings have degraded over time.

 Temperature Fluctuation Effects: Although coastal locations

may experience less extreme temperature swings than inland
deserts, daily and seasonal temperature variations, along with
direct solar exposure on tanks, still cause expansion and
contraction cycles. These cycles impose mechanical stress on
the tank structure and its protective lining system, potentially
leading to fatigue, cracking, or disbondment of linings over
time, exposing the underlying metal to corrosion.

11. Transportation from Khouribga to Jorf Lasfar

(Note: The provided text under this heading describes

transportation from Bou Craa to Laayoune, not Khouribga to Jorf
Lasfar. The text below reflects the content provided.)

Phosphate rock’s transportation to Laayoune

Phosphate rock is transported from the Bou Craa mines to the

processing facilities near Laayoune utilizing one of the world's
longest conveyor belt systems. Spanning approximately 98
kilometers (61 miles) across the Western Sahara desert, this
conveyor belt efficiently moves the phosphate ore to the port area
near Laayoune for subsequent processing, washing, and export.

 Key Features of the Conveyor System:

o Capacity: Designed to transport roughly 2,000 metric tons

of phosphate rock per hour.

o Route: Traverses the desert landscape directly from the

Bou Craa mining area to the coastal processing and port
facilities located south of Laayoune city.

12. Pipeline Transportation from Khouribga to Jorf Lasfar

The transportation of phosphate from the Khouribga mining area to

the Jorf Lasfar processing hub is primarily accomplished via slurry
pipelines. This modern method involves mixing finely crushed
phosphate rock with water to create a slurry, which is then pumped
efficiently over the long distance (approximately 187 km) through
dedicated pipelines.

This pipeline system represents a continuous flow transportation

method, contrasting significantly with static storage conditions. The
constant movement of the slurry introduces distinct considerations,
particularly regarding erosion and corrosion within the pipeline:

 Constant Fluid Movement: Unlike static storage where

sedimentation is a primary concern, the continuous motion
within the pipeline prevents significant settling but introduces
flow-related wear mechanisms.

 Flow-Accelerated Corrosion/Erosion: The constant movement of

the slurry, containing abrasive phosphate particles and
potentially corrosive process water, can physically wear down
the pipe's inner surface. Furthermore, the flow can remove any
naturally forming protective passive films on the metal surface,
continuously exposing fresh material to attack. This combined
erosion-corrosion effect is a major factor in pipeline
degradation.

 Velocity Effects: Flow velocity is not uniform throughout the

pipeline. Higher velocities, particularly in downhill sections
 resulting from the significant elevation drop between the
Khouribga plateau and the coastal Jorf Lasfar site, increase the
shear stress on pipe walls and intensify the rate of erosion-
corrosion.

 Pressure Fluctuations: Pumping stations are required along the

pipeline route to maintain flow. These stations introduce
cyclical pressure variations which can stress the pipeline
material and components, particularly at joints, potentially
accelerating fatigue-related issues or failure mechanisms over
time.

The pipeline system also experiences different flow characteristics

along its length, impacting wear patterns:

 Flow Characteristic Variations:

o Laminar Flow Sections: In long, straight, and level

portions of the pipeline, the slurry flow may tend towards
smoother, more predictable laminar patterns, potentially
leading to more uniform wear patterns.

o Turbulent Zones: At bends, elbows, valves, welds, and

points of diameter change, the flow becomes turbulent
and chaotic. This creates localized areas of high velocity
and intense eddies, significantly accelerating erosion-
corrosion rates in these specific zones.

o Pressure Transition Points: Areas immediately

downstream of pump stations experience higher pressure
and potentially increased turbulence, creating stress
concentrations on the system and potentially accelerating
wear at flanges, connections, and valves.

The continuous nature of pipeline transportation means that even

relatively low rates of erosion-corrosion accumulate constantly over
the pipeline's operational life. This necessitates robust monitoring
programs (like ultrasonic thickness measurements, intelligent
pigging) and proactive maintenance strategies to manage material
degradation and ensure the long-term integrity and safety of this
critical transportation infrastructure.
Okay, here is the text about fertilizer applications formatted using a
mix of paragraphs and bullet points:

13. Applications of Phosphoric Acid in Fertilizer Industry

Phosphoric acid (H3PO4) is a fundamental raw material in the

fertilizer industry, serving as the primary source of phosphorus (P)
for manufacturing several key phosphate fertilizers essential for
modern agriculture.

13.1 MAP (Monoammonium Phosphate)

Monoammonium phosphate (MAP) is a widely used, highly water-

soluble fertilizer providing plants with essential phosphorus (P) and
nitrogen (N).

 Chemical Formula: NH4H2PO4

 Nutrient Content: Typically contains approximately 11%

Nitrogen (N) and 48-55% Phosphorus as P2O5.

Production: MAP is produced through the reaction of ammonia (NH3)

with phosphoric acid (H3PO4).

 Process:

1. Ammonia gas is carefully injected into wet-process

phosphoric acid in a reactor.

2. The exothermic reaction forms monoammonium

phosphate (MAP) slurry or melt.

3. The resulting MAP is typically granulated, dried, and

cooled to produce stable fertilizer granules suitable for
storage, handling, and application.

13.2 DAP (Diammonium Phosphate)

Diammonium phosphate (DAP) is another major phosphate fertilizer,

known for its high phosphorus content and providing both
phosphorus (P) and nitrogen (N). It is one of the most common
phosphatic fertilizers used globally.

 Chemical Formula: (NH4)2HPO4

  Nutrient Content: Typically contains approximately 18%
Nitrogen (N) and 46% Phosphorus as P2O5.

Production: DAP is produced by reacting ammonia (NH3) with

phosphoric acid (H3PO4), using a higher ammonia-to-acid ratio than
for MAP production.

 Process:

1. Ammonia gas is added to phosphoric acid under

controlled conditions, often in multiple stages (pre-
neutralizer and reactor/granulator), to manage the
reaction heat and pH.

2. The reaction forms diammonium phosphate (DAP).

3. The resulting slurry or melt is granulated, dried, and

screened to produce solid DAP granules.

13.3 NPK (Nitrogen-Phosphorus-Potassium) Fertilizer

NPK fertilizers, also known as compound or complex fertilizers, are

multi-nutrient formulations designed to supply a balanced ratio of
the three primary macronutrients: Nitrogen (N), Phosphorus (P,
expressed as P2O5), and Potassium (K, expressed as K2O). They are
tailored to meet the specific nutrient requirements of different crops
and soil conditions.

 General Formula: The nutrient ratio varies widely depending on

the intended use. Common examples include 20-10-10, 15-15-
15, 10-26-26, etc., representing the percentage content of N-P2
O5-K2O.

Production Components: NPK fertilizers are produced by combining

various raw materials that supply the necessary nutrients.
Phosphoric acid (often reacted first to form MAP or DAP) serves as a
primary source of phosphorus.

 Nitrogen sources: (Examples: Ammonia, Urea, Ammonium

Nitrate, Ammonium Sulfate)

 Phosphorus sources: (Examples: Phosphoric Acid, MAP, DAP,

Superphosphates)

 Potassium sources: (Examples: Potassium Chloride (Muriate of

Potash), Potassium Sulfate)
  Process:

1. The selected nitrogen, phosphorus, and potassium

compounds (along with potentially fillers or secondary
nutrients) are mixed or reacted together in the required
proportions to achieve the target NPK grade.

2. The mixture is typically granulated (using methods like

drum granulation or compaction), dried, screened, and
sometimes coated to improve handling properties and
prevent caking during storage.

13.4 TSP (Triple Superphosphate)

Triple Superphosphate (TSP) is another important phosphorus

fertilizer, characterized by its high concentration of phosphorus. It is
particularly suitable for crops with significant phosphorus
requirements or for soils deficient in this nutrient. Unlike single
superphosphate (SSP), it contains very little sulfur.

 Chemical Formula: Primarily Monocalcium Phosphate

Monohydrate (Ca(H2PO4)2⋅H2O, often simplified as Ca(H2PO4)2
).

 Nutrient Content: Typically contains around 44-46%

Phosphorus as P2O5.

Production: TSP is produced by reacting phosphate rock directly

with phosphoric acid (H3PO4). The primary reaction involves
converting the insoluble calcium phosphate in the rock into water-
soluble monocalcium phosphate. Using fluoroapatite as the
representative phosphate mineral, the main reaction is:

Ca5(PO4)3F+7H3PO4→5Ca(H2PO4)2+HF

(Fluoroapatite + Phosphoric Acid → Monocalcium Phosphate +

Hydrogen Fluoride)

 Process:

1. Phosphate rock is finely ground to increase its surface

area and reactivity.
 2. The ground rock is then reacted with wet-process
phosphoric acid (tpically 40-54% P2O5) in a suitable
reactor (e.g., a cone mixer or den).

3. The resulting reaction mass, primarily triple

superphosphate (TSP), requires time to cure (solidify as
the reaction completes) and is then typically granulated,
dried, and screened to produce the final fertilizer product.

Okay, here is
the text about general corrosion factors formatted using a mix of
paragraphs and bullet points:

14. General Corrosion Factors

Corrosion is a critical degradation mechanism affecting materials,

particularly within demanding industrial environments like
Phosphoric Acid Plants (PAP). The performance, reliability, and
lifespan of equipment in such plants are significantly influenced by
corrosion phenomena. This section provides an analysis of potential
corrosion problems relevant to materials used in PAP projects,
covering common corrosion types, key influencing factors specific to
phosphoric acid environments, and standard testing methods.

14.1 Types of Corrosion

Several forms of corrosion can occur in a Phosphoric Acid Plant

environment:

14.1.1 Uniform Corrosion

  Description: General degradation occurring relatively evenly
across the exposed surface of the material.

 Causes: Widespread chemical attack from the acidic

environment, often exacerbated by atmospheric oxygen and
moisture on external surfaces.

 Impact: Gradual thinning of the material over time, potentially

leading to loss of structural integrity if not accounted for in
design (corrosion allowance).

14.1.2 Galvanic Corrosion

 Description: Occurs when two different metals (or alloys) are

electrically connected while immersed in a conductive
electrolyte (like phosphoric acid).

 Causes: The electrochemical potential difference between the

dissimilar metals drives the corrosion process.

 Impact: Preferential and accelerated corrosion of the less noble

(more anodic) metal in the couple.

14.1.3 Pitting Corrosion

 Description: Highly localized form of corrosion that leads to the

formation of small holes or "pits" penetrating into the material.

 Causes: Often initiated by the presence of specific aggressive

ions, particularly chlorides (Cl−) and sometimes fluorides (F−),
which break down protective passive films locally. Common in
phosphoric acid derived from chloride-containing rock or water.

 Impact: Can lead to rapid perforation of equipment (e.g., tank

walls, pipes) with minimal overall material loss, causing
premature failure.

14.1.4 Crevice Corrosion

 Description: Localized corrosion occurring within confined

spaces or crevices (e.g., under gaskets, bolts, deposits, or
between overlapping surfaces).

 Causes: Differences in the chemical environment (e.g., oxygen

concentration, pH, ion concentration) between the crevice and
the bulk solution. Stagnant conditions often promote crevice
corrosion.
  Impact: Can cause severe, hidden damage within joints or
under deposits, potentially leading to unexpected failures.

14.1.5 Intergranular Corrosion

 Description: Preferential corrosion attack along the grain

boundaries of a metallic material.

 Causes: Often related to metallurgical factors, such as

improper heat treatment ("sensitization" in stainless steels)
which can deplete corrosion-resistant elements (like chromium)
at grain boundaries. Can be exacerbated in certain acidic
environments.

 Impact: Leads to a loss of mechanical strength and ductility,

potentially causing cracking or disintegration of the material.

14.1.6 Stress Corrosion Cracking (SCC)

 Description: Formation and propagation of cracks resulting

from the combined influence of tensile stress (applied or
residual) and a specific corrosive environment.

 Causes: Requires a susceptible material, a corrosive

environment (phosphoric acid, potentially containing chlorides
or fluorides), and sufficient tensile stress. Elevated
temperatures often increase susceptibility.

 Impact: Can lead to sudden, often catastrophic failure of

components, frequently without significant prior visual warning
signs.

14.2 Environmental Factors Affecting Corrosion in Phosphoric Acid

Plant

The severity and type of corrosion are heavily influenced by the

specific operating environment:

 Acid Concentration: Generally, higher concentrations of

phosphoric acid increase its corrosivity, although the effect can
vary depending on the material and temperature.

 Temperature: Elevated operating temperatures significantly

accelerate most corrosion reaction rates.

 Impurities: The presence and concentration of impurities

derived from the phosphate rock or process water (especially
 chlorides, fluorides, sulfates, silica, and various metallic ions)
can drastically increase corrosion rates, particularly localized
forms like pitting and crevice corrosion.

 Oxygen Levels: Oxygen availability influences the formation

and stability of passive films. Low oxygen levels within crevices
or under deposits can contribute to localized corrosion.

 Flow Conditions: The velocity and nature (laminar vs.

turbulent) of the flowing acid can impact corrosion. High
velocities or turbulence can lead to erosion-corrosion, where
mechanical wear removes protective films, accelerating
corrosive attack. Stagnant conditions can promote creville
corrosion and corrosion under deposits.

14.3 Corrosion Testing Methods

Evaluating material performance and understanding corrosion

mechanisms often involves various testing methods:

 Salt Spray Testing (primarily for atmospheric corrosion

resistance)

 Electrochemical Impedance Spectroscopy (EIS)

 Potentiodynamic Polarization Scans

 Weight Loss Measurements (Immersion Testing)

 X-ray Diffraction (XRD) for Corrosion Product Identification

 Immersion Testing in specific Phosphoric Acid solutions

(simulating process conditions)

 Slow Strain Rate Testing (SSRT) for SCC susceptibility

Material Selection Study for the Transportation of Phosphoric Acid in
a C5 Corrosivity Site (Laayoune Region)

1. Project Parameters & Operating Conditions

Parameter Value

Phosphoric Acid
54% P₂O₅ (~75% H₃PO₄)
Concentration

Operating Temperature 65 °C

Design Temperature 85 °C

Design Pressure 17 bar g

Atmospheric Conditions ISO 9223 / C5 - Very High Corrosivity

Max Site Temp 50 °C

Min Site Temp 5 °C

Relative Humidity (Design) 80% @ 25 °C

Max Wind Speed 44 m/s

Precipitation Max Daily: 50.4 mm; Annual Avg:

Parameter Value

53.21 mm

Pipe condition exposed

Seismic Zone Zone 1 (Low), RPS 2000 Standard

2. Candidate Materials for Evaluation

 Carbon Steel (CS)

 Stainless Steel 304L

 Stainless Steel 316L

 Stainless Steel 904L

 Alloy 20

 Titanium Gr.2

 FRP (Fiberglass Reinforced Plastic)

 Rubber Lined Steel

 PTFE Lined Steel

 Hastelloy C-276

3. Evaluation Criteria

Criteria Justification

Exposure to 54% P₂O₅ + C5 atmospheric

Corrosion Resistance
environment

Pressure Resistance Must withstand 17 bar g

Temperature
Must handle up to 85 °C
Tolerance

Maintenance Low maintenance materials preferred

Fabrication &
Ease of welding, flanging, joining
Installation
Criteria Justification

Standards
ASME/ASTM compatibility
Compliance

Mechanical Strength Especially under wind and seismic conditions

Evaluation of Carbon Steel (CS)

1. Description of Carbon Steel (CS)

Carbon steel is an iron-carbon alloy with carbon content ranging from 0.1% to
0.6%, without significant amounts of other alloying elements. It is widely
used due to its low cost, good mechanical strength, and ease of fabrication
(welding, forming, machining).

 Types:

o Low carbon steel: < 0.3% C – ductile and easy to weld.

o Medium carbon steel: 0.3–0.6% C – higher strength, reduced

weldability.

o High carbon steel: > 0.6% C – hard and brittle, used in tooling.

 Advantages:

o Very economical and widely available.

o Good mechanical properties for structural use.

o Easy to fabricate and repair.

 Limitations:

o Poor corrosion resistance, especially in acidic and saline

environments.

o Prone to general corrosion, pitting, and stress corrosion

cracking.

o Requires protective coatings or cathodic protection in aggressive

services.

2. Process Conditions Context

  Fluid: Phosphoric acid (H₃PO₄) at ~54% P₂O₅.

 Temperature: Between 65–85 °C.

 Pressure: Up to 17 bar (gauge).

 Atmosphere: Corrosive C5 industrial environment (moist, acidic

vapors).

These conditions are highly corrosive, both internally (acid contact) and
externally (atmosphere), demanding a material with excellent corrosion
resistance.

3. Corrosion Performance of Carbon Steel in Phosphoric Acid

Parameter Performance of CS

Rapid general corrosion. Severe pitting at

Phosphoric acid
>50 °C.

Chlorides (if present) Accelerates corrosion via pitting/crevice.

Operating temp (65– Accelerates corrosion kinetics

85 °C) significantly.

Acid concentration
Beyond CS compatibility range.
(~54%)

 According to corrosion rate data (e.g., NACE MR0175 or Perry’s

Handbook), carbon steel has corrosion rates exceeding 5 mm/year
in hot phosphoric acid > 40% concentration.

 Localized corrosion may result in through-wall failure within

months if unlined and unprotected.

4. Mechanical Suitability

 Strength and pressure tolerance: Carbon steel can mechanically

handle 17 bar, depending on thickness and design.

 ASME B31.3 and Section VIII codes allow for CS in pressure

applications, but not without corrosion allowances or internal
protection.
5. Mitigation Options (and their drawbacks)

Option Drawbacks

Paint/Lining (epoxy, Degradation over time; high

rubber) maintenance.

Cathodic protection Not feasible inside process piping.

Thick corrosion Increases weight/cost, doesn't prevent

allowance failure.

These are only temporary solutions, adding cost and complexity.

6. Industry Practices / Literature Evidence

 Fertilizer, phosphate, and mining industries avoid bare carbon

steel for >40% H₃PO₄, especially above ambient temperature.

 Literature (e.g., Uhlig’s Corrosion Handbook) classifies CS as

unsuitable for hot concentrated phosphoric acid.

 Carbon steel is only used with internal linings or in non-contact

support structures.

7. Final Verdict: ❌ Not Recommended

Criteria Verdict Justification

Corrosion Unacceptable corrosion rates in hot

❌ Poor
resistance phosphoric acid.

Mechanical Can handle pressure, but irrelevant due to

✅ Adequate
strength corrosion failure.

Attractive cost negated by high maintenance

Cost ✅ Low
and short life.

Frequent failures and external repainting

Maintainability ❌ Poor
needed.

Process ❌ Not Total failure expected in months without

compatibility suitable lining.
Evaluation of Stainless Steel 304L (AISI 304L)

1. Material Overview – AISI 304L Stainless Steel

➤ Classification

 Austenitic Stainless Steel (based on Fe-Cr-Ni)

 Designation: UNS S30403, EN 1.4307

➤ Chemical Composition [Ref: ASTM A240, Outokumpu Datasheet]

Typical Content
Element
(%)

Chromium
18.0–20.0
(Cr)

Nickel (Ni) 8.0–12.0

Carbon (C) ≤ 0.03

Manganese ≤ 2.0

Iron (Fe) Balance

➤ Key Characteristics

 Excellent weldability, especially with low carbon to prevent carbide

precipitation.

 Good mechanical strength and ductility.

 Moderate corrosion resistance in mildly aggressive environments.

2. Mechanical Suitability

✅ General Strength Data [Ref: ASME B31.3, ASTM A240]

Property Value

Tensile Strength 485–620 MPa

Yield Strength (0.2% ~170 MPa

offset) (min)

Elongation ≥ 40%
Property Value

Modulus of Elasticity 193 GPa

Design Temp Limit

~425 °C
(ASME)

➤ For our Case:

 Operating Pressure: 17 bar

 Temperature: 85 °C

✔ 304L is mechanically suitable for 17 bar/85 °C service — commonly used

in Class 150/300 piping.
✔ Complies with ASME B31.3 allowable stress limits for design at this
temperature.

3. Corrosion Resistance in Phosphoric Acid

Limited Compatibility in Concentrated H₃PO₄

Key Findings from Studies:

Study / Source Observations

NACE Corrosion SS 304L shows moderate corrosion rates (>0.2

Data Survey mm/year) in 50–70% H₃PO₄ at 80–90 °C.

Avesta Corrosion
304L suitable up to 40–45% H₃PO₄ at 80 °C; at higher
Handbook
concentrations, corrosion increases sharply.
(Outokumpu)

Above 50% H₃PO₄ and 70 °C, 304L begins to pit and

Uhlig’s Corrosion
general attack occurs, especially if contaminants
Handbook
(chlorides, fluorides) are present.

Krochta et al.,
Corrosion rate of 0.4–0.6 mm/year at 85 °C in wet-
Corrosion Science,
process phosphoric acid (54% H₃PO₄).
2002

304L fails to passivate completely in concentrated phosphoric acid at

elevated temperatures, leading to accelerated corrosion.
Failure Mechanisms

Type of Corrosion Susceptibility in 304L

General Acid Attack Moderate to high in H₃PO₄ >50% at >60 °C

Pitting/Crevice
Present, worsens with Cl⁻ or F⁻ contamination
Corrosion

Intergranular Low due to low carbon, but possible if sensitized

Corrosion by poor heat treatment

Stress Corrosion Possible in chloride-containing environments at T

Cracking (SCC) >60 °C

🆚 4. Comparison with More Suitable Alternatives

Alloy 20
Property 304L 316L
(Carpenter 20)

Cr/Ni/Mo content 18-8-0 18-10-2 20-34-3.5

Pitting Resistance Equivalent

~18.3 ~25 >30
(PREN)

Corrosion in 54% H₃PO₄ @ 0.4–0.6 0.05–0.1

<0.02 mm/year
85 °C mm/year mm/year

C5 Atmosphere Suitability Low Medium High

Cost (rel. to CS) ~3x ~3.5x ~6–8x

Although 304L is better than carbon steel, it does not meet the long-
term corrosion resistance criteria for concentrated phosphoric acid at
85 °C nor C5 atmospheric exposure.

5. Lifecycle & Maintenance Implications

Issue 304L Implications

Frequent Expected every 2–4 years in aggressive

replacement service.
Issue 304L Implications

Inspection Annual wall thickness checks likely

frequency required.

Higher due to corrosion-induced leaks or

Shutdowns
failures.

Cleaning
More frequent in outdoor service (C5).
requirements

These risks are not aligned with reliability goals, especially in chemical
processing and continuous operations.

Final Conclusion

Despite being a widely used stainless steel, 304L is not the best choice
due to:

 Insufficient corrosion resistance in concentrated H₃PO₄ at 85 °C.

 Inadequate performance in C5 outdoor/industrial atmosphere.

 Maintenance burden compared to alternatives like 316L or Alloy 20.

 Susceptibility to pitting, SCC, and external rust staining in real

conditions.

 Lifecycle cost is not justifiable versus its marginal improvement

over carbon steel in this environment.

References

1. NACE Corrosion Data Survey – Metals Section, NACE International.

2. Revie, R. W., & Uhlig, H. H. (2008). Corrosion and Corrosion Control, 4th
Ed., Wiley.

3. Outokumpu Oyj. Corrosion Tables and Stainless Steel Selection

Handbook (Avesta).

4. Krochta et al., Corrosion Science, 2002 – "Evaluation of stainless steels

in industrial phosphoric acid."
 5. ASTM A240 – Standard Specification for Chromium and Chromium-
Nickel Stainless Steel Plate.

6. EN ISO 12944-2:2017 – Classification of environments: C1 to C5.

7. API RP 571 – Damage Mechanisms Affecting Fixed Equipment.

Evaluation of Stainless Steel 316L (AISI 316L)

1. Material Overview – AISI 316L Stainless Steel

➤ Classification

 Austenitic stainless steel

 Designation: UNS S31603, EN 1.4404

➤ Chemical Composition [Ref: ASTM A240, Outokumpu Datasheet]

Typical Content
Element
(%)

Chromium (Cr) 16.5–18.5

Nickel (Ni) 10.0–13.0

Molybdenum
2.0–2.5
(Mo)

Carbon (C) ≤ 0.03

Manganese ≤ 2.0

Silicon ≤ 1.0

Iron (Fe) Balance

➤ Key Characteristics

 Superior corrosion resistance over 304L, especially in chloride-

containing or acidic environments.

 Lower carbon content reduces risk of intergranular corrosion after

welding.
  Suitable for chemical processing, marine, and atmospheric
exposure in C4/C5 environments.

2. Mechanical Suitability

Strength Data (Ambient Temperature)

[Ref: ASTM A240, ASME B31.3, EN 10088]

Property Value

485–620
Tensile Strength
MPa

Yield Strength (0.2%) ≥ 170 MPa

Elongation ≥ 40%

Modulus of Elasticity 193 GPa

Hardness (Brinell) ~150 HB

Max Design Temp (ASME

~425 °C
B31.3)

➤ Suitability in Service:

 Pressure: 17 bar

 Temperature: 85 °C

 Standard: Within allowable stress range as per ASME Section VIII,

Div. 1 and EN 13445.

Fully compliant with mechanical design criteria in process equipment and

piping for low to moderate pressures and temperatures up to 400 °C.

3. Corrosion Resistance

➤ Superior in Aggressive Environments

Key Enhancement: Molybdenum (Mo ~2–2.5%)

 Mo boosts pitting resistance, especially in halide-rich and acidic

environments.
a. In 54% Phosphoric Acid at 85 °C

Study / Reference Observation

Avesta Corrosion
316L suitable for 54–60% H₃PO₄ at 85 °C, corrosion
Handbook
rate <0.05 mm/year.
(Outokumpu)

Uhlig’s Corrosion Stable passive film in pure and industrial-grade

Handbook H₃PO₄ up to 85 °C.

316L acceptable in H₃PO₄ up to 80–90 °C for

NACE International concentrations >50%, unless fluorides are
present.

ASM Handbook Vol. Corrosion rate < 0.02–0.05 mm/year in 54% H₃PO₄
13C at 85 °C.

Conclusion:
316L exhibits a low uniform corrosion rate, no pitting, and no cracking
under expected industrial conditions in 54% H₃PO₄ at 85 °C.

b. In Atmospheric Conditions – C5 (EN ISO 12944-2)

Standard / Guide Observation

C5 = highly aggressive urban/industrial

EN ISO 9223 / 12944
atmosphere

316L recommended for C5-I and C5-M

Outokumpu Datasheet
environments without coatings

Pitting Resistance
~25 (vs. 18.3 for 304L) → good pitting resistance
Equivalent (PREN)

✅ 316L performs well in C5 conditions due to its Mo content and stable

passivation layer, especially in marine, coastal, or polluted urban
atmospheres.

Resistance to Other Failure Modes

 316L
Corrosion Type Notes
Resistance

Pitting / Crevice High Mo enhances pitting resistance

Stress Corrosion Improved over 304L, but not

Moderate
Cracking (SCC) immune

L-grade prevents carbide

Intergranular Corrosion Very low
precipitation

Excellent in
General Acid Attack Stable passive layer at 85 °C
H₃PO₄

4. Fabrication & Weldability

Property 316L Behavior Reference

Weldability Excellent ASME Section IX

Filler Metal Used ER316L / E316L AWS A5.9

Post-weld Heat Not required (if properly

ASM Metals Handbook
Treatment done)

Moderate during cold

Work Hardening ASTM A480
forming

Slightly lower than 304 due

Machinability Fair
to Mo

Notes:

 316L resists sensitization due to low carbon.

 Preheating or post-weld heat treatment not required, simplifying

fabrication.

 Widely used in tanks, piping, heat exchangers, and reactors.

Overall, easy to fabricate and weld in chemical plant applications.

5. Cost and Availability

 Relative Cost
Material
(vs. CS)

Carbon
1x
Steel

304L ~2.8–3.0x

316L ~3.5–4.0x

✔️More expensive than 304L, but lifetime cost is lower due to:

 Minimal corrosion

 Fewer shutdowns

 Low maintenance

Final Conclusion – Why 316L Is a solid candidate

316L offers an optimal balance of corrosion resistance, mechanical

integrity, weldability, and cost-effectiveness for your application.

Reasons for Selection:

Criteria Justification

Corrosion Suitable for 54% H₃PO₄ @ 85 °C with proven low

Resistance corrosion rates

Atmospheric
Performs well in C5 marine/industrial conditions
Resistance

Mechanical
Fully compliant with ASME & EN design rules
Suitability

Weldability &
No PWHT, excellent weldability, widely supported
Fabrication

Availability Readily available, standardized, proven in industry

References

1. Outokumpu Stainless Steel Corrosion Tables & Datasheets

2. ASTM A240 / ASME SA240 – Specification for 316L Plate & Sheet
 3. ASM Handbook Volume 13C – Corrosion: Environments and
Industries

4. NACE MR0175 / ISO 15156 – Materials for Use in H₂S

Environments

5. Revie, R. W., & Uhlig, H. H. (2008). Corrosion and Corrosion Control,

Wiley.

6. EN ISO 12944-2 – Corrosivity Categories (C1–C5)

7. Avesta Research Centre – Material Selection Guide for Chemical

Industry

8. API 571 – Damage Mechanisms Affecting Fixed Equipment in the

Refining Industry

Evaluation of Stainless Steel 904L

1. Material Overview – AISI 904L Stainless Steel

➤ Classification

 High-alloy austenitic stainless steel

 Designation: UNS N08904, EN 1.4539

➤ Chemical Composition [Ref: ASTM B625, Outokumpu]

Typical Content
Element
(%)

Chromium (Cr) 19.0–23.0

Nickel (Ni) 23.0–28.0

Molybdenum
4.0–5.0
(Mo)

Copper (Cu) 1.0–2.0

Carbon (C) ≤ 0.02

Iron (Fe) Balance

➤ Key Characteristics
  Designed for superior corrosion resistance in strong acid
environments.

 Excellent resistance to sulfuric acid due to its high Ni, Cr, Mo, and
Cu content.

 Often used in fertilizer plants, acetic acid, and strong reducing

acids.

2. Mechanical Suitability

Strength Data (Ambient Temp)

[Ref: ASTM B625, ASME Section II]

Property Value

≥ 490
Tensile Strength
MPa

Yield Strength ≥ 220

(0.2%) MPa

Elongation ≥ 35%

Modulus of
195 GPa
Elasticity

Hardness (Brinell) ~150 HB

Mechanically acceptable for pressure (17 bar) and temperature (85 °C)
according to ASME B31.3 and EN 13445.

🔻 However:

 Yield strength is lower than duplex or super-austenitic alternatives.

 Mechanical advantage over 316L is minimal, despite higher cost.

3. Corrosion Resistance

a. In 54% Phosphoric Acid at 85 °C

Source / Study Observations

Avesta 904L shows excellent corrosion resistance in pure

Source / Study Observations

phosphoric acid, comparable to 316L in medium

Handbook
concentrations.

Outokumpu Corrosion rate in 54% H₃PO₄ @ 85 °C ≈ <0.01 mm/year,

Corrosion Tables similar to 316L.

NACE Paper No significant advantage of 904L over 316L unless

03108 (2003) fluoride, chloride, or sulfur compounds are present.

Uhlig’s 904L performs best in mixed acid systems, particularly

Handbook H₂SO₄, not pure H₃PO₄.

904L is corrosion-resistant — but so is 316L in this specific case.

Conclusion: Over-specified for 54% phosphoric acid without significant gain

in corrosion resistance compared to 316L.

4. Limitations & Reasons for Rejection

Factor 904L Issue

Cost ~6–8x Carbon Steel Very expensive

Gain vs 316L Minimal in this case No added benefit in 54% H₃PO₄

Tricky (requires Dilution during welding affects

Weldability
special filler) corrosion behavior

More limited than

Availability Longer lead times
316L

Mechanical
Not significant Similar to 316L
Superiority

SCC & Pitting

High But not necessary for this case
Resistance

5. Fabrication & Weldability

Property 904L Behavior

Weldability Moderate — requires control

Property 904L Behavior

Filler Metals ER385 (AWS A5.9) or 904L-specific

Yes — may reduce corrosion resistance at

Dilution Risk
the weld

Post-Weld Heat Not required, but pickling highly

Treatment recommended

Forming Difficult — high Ni & Mo cause springback

Machinability Poor compared to 316L

Requires experienced welders and cleanroom-style fabrication

procedures to retain corrosion properties.

6. Cost and Value

Materi Cost Multiplier

Note
al (vs. CS)

316L ~3.5–4.0x Cost-effective

Much higher price, no extra value in

904L ~6–8x
this case

Total lifecycle cost unjustified unless extreme acid conditions (e.g.

chlorides + H₂SO₄) or full immersion in seawater.

Final Conclusion

Although 904L performs well in many aggressive environments, it is not

optimal due to the lack of significant advantages over 316L for:

 54% phosphoric acid at 85 °C, where 316L performs equally well

 C5 atmospheric exposure, where 316L is sufficient

 Mechanical and welding performance, which does not exceed 316L

meaningfully

Summary Table – Rejection Justification

 904
Criteria Verdict
L

H₃PO₄ Resistance ✔️ Equal to 316L

Atmospheric
✔️ Equal to 316L
Corrosion

Mechanical Similar to
✔️
Properties 316L

Fabrication & More

⚠️
Weldability demanding

Cost ❌ Much higher

Less
Availability ⚠️
accessible

Overall Benefit ❌ Not justified

References

1. Outokumpu Stainless Steel Corrosion Tables –

www.outokumpu.com

2. Avesta Corrosion Handbook

3. ASTM B625 – 904L Specification

4. Revie & Uhlig, Corrosion and Corrosion Control, 4th Edition

5. NACE Paper 03108, 2003 – 904L vs 316L in H₃PO₄ and H₂SO₄

Environments

6. ASM Handbook, Volume 13C – Corrosion: Environments and Industries

7. EN ISO 12944 – Atmospheric corrosion classifications

Detailed Study: FRP (Fiberglass Reinforced Plastic) - Evaluation and

Selection

1. Material Overview - FRP (Vinyl Ester Resin Based)

  Classification: Composite material consisting of reinforcing glass
fibers embedded in a thermosetting polymer resin matrix. For this
application, Vinyl Ester resin is specified due to its superior chemical
resistance compared to general-purpose polyester resins.

 Designation: Varies by manufacturer and specific standard (e.g.,

conforming to aspects of ASME RTP-1, ASME NM.2, ISO 14692, ASTM
D3299).

 Key Components:

o Resin: Vinyl Ester (provides chemical resistance and binds

fibers).

o Reinforcement: Glass fibers (e.g., E-glass, ECR-glass) provide

strength and stiffness. Formats include chopped strand mat,
woven roving, continuous filaments.

o Corrosion Barrier: A resin-rich inner layer, often reinforced with

a C-glass or synthetic veil, provides the primary chemical
resistance.

 Key Characteristics:

o Excellent corrosion resistance to a wide range of chemicals,

including phosphoric acid.

o High strength-to-weight ratio; significantly lighter than steel.

o Electrically non-conductive.

o Can be tailored (resin selection, reinforcement type/orientation)

for specific applications.

o Low thermal conductivity.

2. Mechanical Suitability

 General Strength Data: Mechanical properties (tensile strength,

flexural strength, modulus) vary significantly based on resin type, fiber
type, fiber content, orientation, and manufacturing process. Typical
values for Vinyl Ester FRP laminates might include:

o Tensile Strength: 100 - 300 MPa (highly dependent on fiber

orientation)

o Flexural Strength: 150 - 400 MPa

 o Modulus of Elasticity: 7 - 20 GPa (significantly lower than steel)

 Suitability in Service:

o Pressure: 17 bar g. FRP piping and equipment can be designed

and fabricated to withstand this pressure, requiring specific
engineering calculations based on standards like ASME NM.2 or
ISO 14692 to determine required wall thickness, laminate
structure, and joint design. Pressure rating is highly dependent on
diameter and temperature.

o Temperature: Design temperature up to 85∘C. High-quality Vinyl

Ester resins generally maintain good mechanical properties and
chemical resistance up to approximately 100∘C, making them
suitable for the 85∘C design temperature. Derating factors for
strength at elevated temperatures must be applied during
design.

 Standards Compliance: While not directly covered under metallic

codes like ASME B31.3 in the same way, FRP design and fabrication are
governed by specific standards such as ASME RTP-1 (Reinforced
Thermoset Plastic Corrosion-Resistant Equipment) and ASME NM.2
(Glass-Fiber-Reinforced Plastic Piping), which provide rules for design,
fabrication, inspection, and testing.

3. Corrosion Resistance

 a. In 54% Phosphoric Acid at 85∘C:

o Vinyl Ester resins are known for their excellent resistance to

acids, including phosphoric acid, across a wide range of
concentrations and temperatures.

o Unlike metals, FRP does not rely on a passive film and is

generally immune to uniform corrosion in this service.

o Resistance to pitting and crevice corrosion mechanisms common

in metals is inherently high due to the non-metallic nature.

o Proper resin selection (e.g., Bisphenol-A epoxy vinyl esters,

Novolac vinyl esters) is crucial, but standard Vinyl Esters typically
perform well in 54% H3PO4 up to 85∘C. Impurities in the acid
should be considered, but Vinyl Esters generally offer broad
resistance.
  b. In Atmospheric Conditions - C5 (EN ISO 12944-2):

o FRP is inherently resistant to atmospheric corrosion, including the

aggressive saline and industrial C5 environment. It does not rust
or suffer from galvanic corrosion.

o UV radiation from sunlight can degrade the resin surface over

time. For outdoor applications in C5 environments, incorporating
UV inhibitors in the outer resin layer or applying a UV-resistant
topcoat (e.g., gel coat, paint) is standard practice for long-term
durability.

4. Fabrication & Installation

 Methods: FRP components (pipes, tanks, ducting) are typically

manufactured using methods like filament winding (for pipes and
cylindrical tanks), hand lay-up, or spray-up (for complex shapes,
fittings, tank shells/roofs).

 Joining: Piping systems are joined using methods like:

o Butt-and-wrap joints (adhesive bonding with overwrapped

laminate layers).

o Socket / Bell-and-spigot adhesive joints.

o Flanged connections (using FRP flanges or metallic flanges stub-

ended with FRP).

 Installation:

o Significantly lighter weight compared to steel simplifies handling,

transport, and installation, potentially reducing equipment and
labor costs.

o Requires careful handling to avoid impact damage during

installation.

o Proper jointing procedures are critical and require skilled, certified

technicians. Adhesive curing times and conditions must be
strictly followed.

o Requires appropriate support spacing due to lower stiffness

compared to steel.

5. Limitations & Considerations

  Impact Resistance: FRP can be susceptible to damage from impacts,
potentially causing cracks or delamination.

 Abrasion Resistance: If the phosphoric acid contains abrasive solids

(slurry), the relatively soft resin matrix can be subject to wear.
Abrasion-resistant liners might be needed in such cases.

 Quality Control: Performance relies heavily on proper design, material

selection, manufacturing quality control (e.g., cure verification, void
control), and correct installation/joining procedures.

 Creep: FRP exhibits creep (deformation under sustained load)

especially at elevated temperatures, which must be considered in
design, particularly for pressure applications and support spacing.

 Repair: Repairs (e.g., laminate patching) are possible but require

specialized knowledge and procedures.

6.Availability

Availability: Readily available from numerous specialized FRP fabricators

worldwide. Custom components require lead times for design and
manufacturing.

7. Final Conclusion – Why FRP Is a solid candidate

Vinyl Ester based FRP is selected as a primary material of construction,

particularly for lower-pressure applications within the project, based on its
compelling advantages:

 Excellent Corrosion Resistance: Provides outstanding resistance to

both the internal 54% phosphoric acid at 85∘C and the external C5
atmospheric conditions.

 Cost-Effectiveness: Offers a significantly lower cost alternative

compared to high-nickel alloys or titanium, while providing superior
corrosion performance to standard stainless steels in this specific
environment.

 Low Maintenance: Requires minimal maintenance due to its inherent

corrosion resistance.

 Design Flexibility: Can be engineered to meet the required pressure

(17 bar g) and temperature (85∘C) conditions.

 Lightweight: Facilitates easier and potentially less costly installation.

While 316L stainless steel is chosen for high-pressure metallic sections, FRP
(Vinyl Ester) provides an optimal solution for components like above-ground
pipelines, storage tanks, scrubbers, and vent lines, contributing to a cost-
effective and durable hybrid material approach for the project.

Rationale for Hybrid Material Selection (316L Stainless Steel and

Vinyl Ester FRP)

While both 316L Stainless Steel and Vinyl Ester FRP demonstrate suitable
corrosion resistance to 54% phosphoric acid at the design temperature
(85∘C) and the external C5 atmospheric conditions, the decision to use a
hybrid approach stems from optimizing the material selection based on
varying demands and properties relevant to specific locations within the
piping system. The same fluid is transported, but the mechanical stresses,
connection types, installation complexities, and cost implications differ across
the system.

1. Mechanical Strength, Pressure Containment, and Stress

Concentration:

o 316L SS: Offers well-defined, high mechanical strength (tensile,

yield), toughness, and stiffness characteristic of metals. It is
inherently robust for handling the 17 bar g design pressure and
potential surges or vibrations. Its isotropic nature provides
predictable behavior under stress. This makes it the preferred
choice for sections demanding the highest mechanical integrity,
such as:

 High-pressure lines directly from pumps.

 Areas subject to higher vibration or mechanical loads.

 Zones with significant stress concentrations, like flanged

connections or sharp bends where metallic ductility might
be advantageous.

o FRP (Vinyl Ester): While FRP can be engineered to handle 17

bar g pressure through appropriate laminate design (fiber
orientation, thickness), its mechanical properties are highly
directional and different from metals. It has a lower modulus of
elasticity (less stiff) and is more susceptible to damage from
impact or point loads. Its pressure rating is highly dependent on
diameter, temperature, and specific construction. Therefore, it is
often selected for sections where pressure demands are
 consistent and high mechanical stress concentrations are less
likely, such as straight runs of above-ground pipe.

2. Fabrication, Connections, and System Integration:

o 316L SS: Benefits from standardized, well-established metallic

fabrication techniques, primarily welding. This allows for complex
configurations, precise dimensional control, and robust, easily
inspectable joints. Metallic flanged connections are standard and
reliable for high-pressure sealing and integration with metallic
equipment like pumps, valves, and instruments.

o FRP (Vinyl Ester): Joining typically involves adhesive bonding

(e.g., butt-and-wrap, socket joints) or FRP flanges. While effective
when done correctly, these methods require specialized skills,
strict adherence to procedures (surface prep, adhesive mixing,
curing times/temps), and may be more challenging for complex
geometries or field modifications compared to welding steel.
Adhesive joints can also be a point of concern under high stress
or fatigue conditions. Therefore, 316L is often preferred at
complex connection points or where frequent
disassembly/reassembly might occur.

3. Corrosion Resistance and Maintenance:

o 316L SS: Offers adequate corrosion resistance to 54% H3PO4 up

to 85∘C and good resistance to C5 atmosphere. However,
stainless steels can still be susceptible to localized corrosion
(pitting, crevice) if aggressive contaminants (like chlorides, which
might be present in industrial H3PO4) exceed certain limits, or
under specific conditions (e.g., under deposits). It offers good, but
not absolute, immunity.

o FRP (Vinyl Ester): Provides excellent, often superior, corrosion

resistance to both the acid and the C5 atmosphere. It is immune
to galvanic corrosion and generally more resistant to pitting and
crevice attack than 316L in this service. This leads to very low
maintenance requirements, as external painting isn't needed for
corrosion protection, and internal degradation is minimal. This
 makes FRP highly desirable for long, exposed runs where
maintenance access might be factored in.

4. Cost-Effectiveness (Lifecycle Cost):

o 316L SS: Represents a moderate cost among corrosion-resistant

alloys – more expensive than carbon steel but considerably
cheaper than higher alloys like 904L, Alloy 20, or Titanium.

o FRP (Vinyl Ester): Generally less expensive than high-nickel

alloys and potentially offers lower installed costs than 316L in
some scenarios (e.g., large diameter pipes, tanks) due to its
lighter weight. Its major advantage lies in lower lifecycle costs
due to minimal corrosion and maintenance.

o Hybrid Approach: Using 316L only where its superior

mechanical properties or fabrication suitability are essential, and
using FRP for the bulk of the system (long pipe runs, tanks, etc.),
provides an optimized balance. It avoids the high expense of
using special alloys throughout while leveraging FRP's corrosion
resistance and lower maintenance where feasible, leading to the
most cost-effective overall solution for the required performance
and lifespan.

Rationale for
316L Stainless FRP (Vinyl Ester Hybrid Choice /
Feature
Steel Based) Typical Use in
System

Adequate to Both suitable, FRP

Excellent for 54% H3
Internal Corrosion Good for 54% offers superior
PO4 @ 85°C
H3PO4 @ 85°C resistance overall.

Both suitable, FRP

External Corrosion (C5) Good resistance Excellent (Immune) requires no
external protection.

316L: Preferred for

High, robust, Good, but lower
high
Mechanical Strength ductile, high stiffness & impact
stress/vibration
stiffness resistance than steel
zones.

316L: Used where

Inherently
Pressure Handling (17 Can be engineered, pressure integrity
suitable, well-
bar) design-dependent is most critical
defined limits
(pumps).
 Standard 316L: Used for
Specialized
welding, easy complex areas,
Fabrication/Connections bonding/wrapping;
for complex flanges, equipment
lightweight install
parts/flanges tie-ins.

Low, potential FRP: Advantage

Maintenance monitoring Very Low for long runs, less
needed accessible areas.

Balances initial
Moderate (vs. Moderate (vs.
Cost (Initial) cost across the
CS/High Alloys) CS/High Alloys)
system.

Potentially Lower Hybrid: Aims for

Cost (Lifecycle) Good (due to less optimal lifecycle
maintenance) cost.

High-pressure
Above-ground Use each material
sections, pump
Typical Application pipelines, tanks, where its strengths
discharge,
scrubbers, vents are best utilized.
flanged zones