Colloquium

Summer Internship @ Reliance Industries Limited Harsh Kumar Singh (2010ME10678)

Introduction to Reliance Industries Limited

The Reliance Group was founded by Dhirubhai H. Ambani (19322002) It is India's largest private sector enterprise with businesses in the energy and materials value chain. Chairman and Managing Director: Mukesh Ambani Group's annual revenues are in excess of US$ 66 billion.

Updated 2006-07

CHLOR-ALKALI
Products:
Chlorine (Primary Product) Hydrogen Sodium hydroxide (caustic) solution.

 PROCESS FLOW DIAGRAM

Salt chemicals
Primary Brine Secondary Brine

98% H2SO4

Cl2 Treatment

HCl Unit CHLORINE CAUSTIC

H2 Unit

HCL
HYPO

Rectifo rmer Power

G CELL

HOUSE Waste Air Dechlorination

HYDROGEN
78% H2SO4

Utilities

Anolyte Dechlorination

Catholyte system

CEU Waste water Treatment L

CCU

SOLID WASTE LIQUID WASTE SCRUBBED NON TOXIC GAS

Project :
Failure Study Of FRP Piping At Chlor-alkali Plant

SCOPE :
Study failure of FRP piping at Chlor-Alkali plant & Collect failure data & Study type of failure

Materials:

Classification of Composite

WHAT IS FIBER- REINFORCED PLASTICS (FRP)?

Fiber reinforced polymers are made of two primary constituents; fibers and a polymer matrix. The structure gives completely different chemical and physical properties than the properties of the individual materials. Apart from this additives can give additional properties like colour, UV protection, flame retardant nature etc.

WHY FRP ?
Infinite potential Low weight: Mechanical strength High impact strength Formability Chemical resistance Corrosion resistance Thermally insulating Fire resistance

FRP Piping @ CA plant DMD

Specification by : UDHE India Largest subsidiary in the ThyssenKrupp Uhde network Specification includes:
Manufacturing standards Pipeline designation Temperature and pressure ratings Welding procedure for lined and non-lined FRP pipes

FRP piping in CA PLANT

S no. 1 2 3 Piping Class PD31 Resin Used Alpolit-745 S Liner Polyvinyldiflouride(PVDF) Polypropylene(PPH) Polyvinylchloride(PVC) PL31/ PL31A/ PL31B/ Alpolit-745 S PL31C PQ31/ PQ31A/ CPol-3601 PQ31B/ PQ31C/ PQ31E/ PQ31F PR31/ PR31A Derakane 411-45 PW31 Alpolit UP797

4 5
6

----------

PX31/ PX31A/ PX31B/ Altac-382 PX31C/ PX31D/ PX31E/ PX31F

S no. 1 2 3 4 5
6

Piping Name PD31 PL31 PL31A PL31B PL31C

PQ31

Designed Pressure(psi) 4.0 0.4 8.0 7.0 3.5

3.0

Designed Temp.(oC) 95 95 80 95 80
60

Application Area Acidified Brine H2 at Cell to Stack Pure Brine (after Ion-exchange Column) Caustic Solution in Cell House Pure Brine (after Ion-exchange Column)
Waste Water Containing Chlorine

3.5 0.4 7 8 9 10 PQ31A PQ31B PQ31C PQ31E 3.0 6.0 4.0 3.0 0.4 0.1

60 60 60 65 60 60 60 60

33% HCL Acid Chlorine Waste Moist Air Waste Water from Pump Flushing DM water Sodium Bisulphate Waste Water Chlorine Free Chlorine Waste Air Moist Containing H2SO4 Chlorine Waste Air Containing HCL

Quantum of FRP Piping

Inch-Metre (INM) = It is defined as the multiplication of diameter of pipe (in inches) and length of pipe (in metres). It reflects the quantity of the piping that is required for a particular unit. Inch-Diameter (IND) = It is defined as the multiplication of diameter of pipe (in inches) and number of joints present in the pipeline. It represents the amount of work that is to be done on installed of a pipeline. It is best suited to minimize IND for installation of pipeline.

Total INCH-METER
Calculated using Microsoft Excel Includes over 750 pipelines
FRP HT (PW class) FRP PP & PPH lined (PL class) FRP PVC lined (PQ class) FRP PVDF lined (PD class) FRP Resin Altac-382 (PX class) FRP V (PR class) = = = = = = 7974.35 18181 7315.3 109.2 15347.6 2216.75 INM INM INM INM INM INM

Total INM = 51144.2 INM

Properties of FRP piping

1. Liner
PVC (Polyvinyl Chloride) PP (Polypropylene) PVDF(Polyvinylidene Fluoride)

2. Resin
Different type of resins Timeline of resins

Liner
Characteristics

PVC (Polyvinyl Chloride) PP (Polypropylene)

Excellent mechanical and PP is light weight and chemical resistance high in chemical properties at low cost resistance. 0 to 60C -20 to 90C

PVDF (Polyvinylidene Fluoride)

Superior chemical resistance and abrasion resistance. -40 to 120C

Working temperature range High chemical resistance towards

98% H2SO4, dry chlorine and low pressure wet chlorine gas

alkalis, salts, organic solvents and most acids, particularly hydrochloric and phosphoric acid.

halogens such as chlorine and bromine, strong acids such as hydrofluoric and nitric acids, organic solvents and oils.

Low chemical resistance towards

chlorinated hydrocarbons, ketones and esters

strong acids, chlorinated hot bases hydrocarbons, aromatic compounds and high concentrations of free chlorine.

Chemical Resistance Chart for liners

Chemical Compound Ammonia Gas (NH3 up to 60 oC) Barium Carbonate (BaCO3 up to 60 oC) Barium Sulphate (BaSO4 up to 60 oC) Calcium Chloride (CaCl2 up to 60 oC) Calcium Carbonate(CaCO3 up to 60 oC) Chlorine Gas Cl2 (wet & 60 oC ) Chlorine Gas Cl2 (wet & 100 oC ) Chlorine Gas Cl2 (up to 150 ppm moisture & 60 oC) Chlorine Gas Cl2 (up to 150 ppm moisture & 100 oC) PVC A A A A A B --A --PP A A A A A X X X X PVDF A A A A A A A A A

Resin
Timeline of resins
Bisphenol A Fumarate polyester resin Chlorendic acid polyester resin (improvement in corrosion performance )

Polyester

Bisphenol A vinyl ester resin (more resistant to thermal and mechanical stress) Epoxy novolac vinyl ester resin (enhanced resistance to organic solvents and higher Epoxy Vinyl working temperature) Ester Brominated epoxy vinyl ester resin ( fire retardance in addition to corrosion resistance )

Resins Used @ CA plant

1. Altac 382: propoxylated bisphenol A fumarate unsaturated polyester resin 2. Alpolite UP 745/56: teraphthalic acid/neopentyl glycol resin 3. Aloplite UP 797: chlorendic acid/ neopentyl glycol resin 4. CPOL 360: Isophthalic Acid/neopentyl glycol resin 5. Derakane 411-45: bisphenol-A epoxy resin

Selection of Resins
It is done with the help of chemical resistance table. Example:
Ashland, Derakane epoxy vinyl ester resins chemical resistance guideResin selection guide for corrosion resistant applications Vipel, Vinyl Ester Resin Guide-To Corrosion Resistant Vipel Resins DSM, Durability & Protection- Guide to Chemical Resistance Reichhold, DION Corrosion Guide

DEFECTS IN COMPOSITE
1. Delamination: It refers to situations in which failure (or inadequate adhesion) occurs on a plane between adjacent layers within a laminate. Reason: inadequate resin concentration cracks

2. Cracking: It is a discrete single crack type defect in the composite usually through thickness and normally affecting both matrix and fibers. Reason: It mostly occur as part of the curing Process under the thermal or residual stresses induced hole drilling and trimming impact damage Surface cracking can arise from impact damage or environmental degradation

3. Disbond : The term disbond here is defined as a separation of the the composite material from another material to which it has been adhesively bonded. Reason: Inadequate resin

4. Porosity and voids At Microlevel : porosity At Macrolevel : voids Reason: entrapped air, moisture or volatile products

In-Field Defects in FRP piping

1.

2.

3.

4.

5. Ageing Damage Average industrial life of FRP Pipes: 8-10 years It includes: a) Surface Attack b) Stripping c) Mud-Cracking d) Erosion/Corrosion e) Permeation f) Osmotic Blistering

Failure Data Analysis

1. Study of Database from SAP system 2. Root and Cause Analysis

Study of Database from SAP system

Duration : 01/01/10 to 07/06/13

S no.
1 2 3 4 5 6 7 8 CHU CHU-ELS CLU-CCD CLU-CLL SBU SBU-ADC SBU-CDC SBU-SBP

UNIT

Number of failures
17 34 17 5 68 21 24 25 TOTAL 211

CONCLUSION FROM STUDY OF SAP DATABASE

Types of most common defects identified from SAP database: Pinhole:- because of entrapping of air bubbles Impact crack:- because of high magnitude impacts, concentrated resin at one spot and insufficient reinforcement Delamination:- because of poor glass saturation, too high glass concentration and failure to remove air-inhibition coat before adding layers. Ageing Damage

Conclusion & Recommendation

For newly installed FRP pipes( less than 3 years): Causes behind failure : Manufacturing defects and poor workmanship in case of leakage. Manufacturing defects: it includes poor bonding strength, high volume fraction of voids, improper glass reinforcement, improper distribution of resin while pipe production, insufficient curing time, moisture entrapment etc.

For formerly installed FRP pipes (more than 3 years): Cause behind failure : Ageing failure, impact cracks and environmental factors.

1. Inclusion of volume fraction of voids in certification of pipes.

higher volume fraction of voids

higher the porosity and permeability Also reduction in mechanical properties

shorter the life of FRP pipes

Reference: R. M. V. G. K. Rao & N. Balasubramanian(2001) Moisture Absorption Phenomenon in Permeable Fiber Polymer Composites, Indian Institute of Science. It can be generalized that higher the volume fraction of voids in a composite lowers the volume fraction of fibers and higher the diffusivity which in turn decreases the durability and longevity of FRP pipes.

2. To follow standard welding procedure for FRP pipes and skilled workmanship
S no. 1. Specified Practice as per UDHE Actual Practice

For a good joint the pipe end must be sanded with After cutting, to be weld surface is not cleaned sandpaper or right angle grinder. Keep it free of oil, fat appropriately using sand paper and nor it is or water. wiped to remove dust and dirt. All cut edges must be coated with a mixture of resin and No such coating is applied hardener before positioning for joining. Pipe is clamped Clamp is not provided to support pipe. It although depends on the space for support/clamp. Resins must be mixed with prescribed % of hardner, These are mixed by just sheer anticipation. Initiators, Promoters, and Accelerators. Higher % of accelerator reduces gel time. Lesser % increases gel-time leading to improper bonding. Higher % of initiator leads to faster curing leading to insufficient time for application of resin. Lesser % initiator doesnt lead to full curing.

2.

3.

4.

5.

Filler cement eg Maxhesive should be used Not used. before strapping FRP layers

6.

Roller should be used to roll out any trace of Most of the work is done by brush air bubble from coated glass fiber with only. catalysed resin. Air bubbles lead to formation of voids and these lead to pin hole, debonding and delamination.

7.

If there is any wrinkle formation then it must Wrinkles are be removed removing it.

strapped

without

3. To maintain storage condition of resins and fibers as per certification.

Keep moisture away from all parts and materials. Moisture inhibits cure and affects bond.

Inspection
In Chlor-Alkali DMD Complex: Visual inspection for detection of any signs of cracks, pits, rust, or corrosion(main testing). Burst test to test pipelines for strength and leaks. The test involves filling the vessel or pipe system with a liquid, usually water, which may be dyed to aid in visual leak detection, and pressurization of the vessel to the specified test pressure. The location of a leak can be visually identified more easily if the water contains a colorant. Strength is usually tested by measuring permanent deformation of the container. Borcol hardness tester to indicate the completeness of resin cure in FRP laminates.

In-process Inspection:

1. Ultrasonic Testing
To quickly and accurately measure the thickness of FRP parts and find defects Principle: ultrasonic waves penetrate materials at different speeds depending on their density and type. In case of cracks or voids, ultrasonic devices can pick-up arrival time of the reflected waves and estimate the location of voids. It also can be used for thickness measurement.

2. Acoustic Emission
Acoustic emission testing identifies and locates active defects in laminates by detecting minute acoustic impulses that are generated as a defect propagates under load.

Thank you..!!