POLLUTION PREVENTION

IN
UNIT OPERATIONS & UNIT
PROCESSES
(1)

Dr Ir Jay Nambiar
The Keeling Curve
CO2 levels
 GENERAL GLOBAL TRENDS
• Exponential rise in human population leading
to Increasing pressure on Natural Resources:
Air and Water
Arable Land
Raw Materials
• Modern societies have ever increasing
demand for industrial chemicals
IMPACT OF INDUSTRIAL CHEMICALS (i)

• POSITIVE IMPACT

 Raised standard of living

 Prolonging human life
 Improving environment
IMPACT OF INDUSTRIAL CHEMICALS (ii)

• NEGATIVE IMPACT (as newer chemicals are

introduced and existing ones continue to be
used)

 Impact on health and environment is a major

concern
 ENVIRONMENTAL OBJECTIVES ARE
CRITICAL IN CHEMICAL PROCESS DESIGN

• Challenge of future generations of Chemical

Engineers is:

Develop and master Technical Tools that

will integrate environmental objectives
into design decisions
 EXAMPLE FROM RUBBER INDUSTRY
Zinc Oxide
• Stringent regulations related to Zinc in
effluent discharge from rubber products
manufacture down to 2ppm level
• Tyre particles/dust from wear and tear on
road surfaces leading to chemicals used in
tyre manufacture leaching into waterways.
 RUBBER PRODUCTS MANUFACTURE
SECTORS
• Tyres
 RUBBER PRODUCTS MANUFACTURE
SECTORS
• Industrial & General Rubber Goods
 RUBBER PRODUCTS MANUFACTURE
SECTORS
• Latex Products
SULPHUR VULCANIZATION OF RAW RUBBER

• Since commercial discovery of Vulcanization

by Charles Goodyear (ca. 1839), Sulphur still
remains the principal vulcanizing ingredient
 EFFECT OF VULCANIZATION ON
RAW RUBBER (i)
• Chemical crosslinking between polymer
chains
• Leads to improved durability, resilience,
resistance to thermal aging, stiffness etc.
• Permits usage of rubber in a wide range of
applications as diverse as pneumatic and
solid tyres, bridge bearings, tank linings,
gloves, catheters etc.
 CROSSLINK STRUCTURE – CV SYSTEMS
•  
•  
•  
•  
•

S
•  
•  

• SX
•    SY
S S
•  
•  
•  
•  
CROSSLINK STRUCTURE – EV SYSTEMS

S2 S
ROLE OF ZNO IN VULCANIZATION
• In rubber products manufacture, raw rubber
is intimately mixed with several ingredients
including chemicals that form the
vulcanization system
• ZnO is a key element of the vulcanization
system – it ACTIVATES sulphur vulcanization
and reduces vulcanization time
ZINC OXIDE CONSUMPTION BY INDUSTRY

Rubber
Ceramics
Chemical
Agricuture
Paint
Other
ZINC OXIDE USE IN RUBBER INDUSTRY
• > 60 % ZnO world production goes into Rubber
Products Manufacture + Latex Preservation
• Usage levels typically 3-5 p.h.r. in rubber
compounding
• Annual consumption of rubber (natural +
synthetic) currently = 25M tonnes
• ± 1M tonnes/year ZnO used in the rubber
industry
STEPS IN SULPHUR VULCANIZATION
accelerator + ZnO

zinc-accelerator complex
S8
Acc-SX-Zn-SX-Acc or polysulphidic accelerator
rubber
rubber-SY-Acc

rubber-SY-rubber

rubber-SZ-rubber
ZnO LEVELS IN RUBBER PRODUCT
MANUFACTURE (i)
• Truck Tyre Retread Compound
Ingredients Level (p.h.r.)
Natural Rubber (SMR 20) 100
ZnO 3
Stearic Acid 2.4
Carbon Black (N220) 53
Oil 8
Wax 1
Anti-oxidant 2.4
Anti-ozonant 1.5
Accelerator 1.5
Sulphur 1.5
ZnO LEVELS IN RUBBER PRODUCT
MANUFACTURE (ii)
• Nitrile Glove Compound
Ingredients Level (p.h.r.)
XNBR Latex 100
SDS 0.2
KOH 1.8
Sulphur 1.0
ZDBC 0.7
ZnO 1.5
 ZnO LEVELS IN RUBBER PRODUCT
MANUFACTURE (iii)
• Natural Rubber Latex Compounds
  Surgical Gloves Condoms
Ingredients (p.h.r.) (p.h.r.)
Natural Rubber 100 100
Latex
KOH 0.50 0.25
ZnO 2.0 0.5
Accelerator 2.0 1.0
Sulphur 0.25 2.5
 BENEFITS TO RUBBER INDUSTRY IN
REDUCTION OF ZnO USAGE
• Lower production cost

• Meet increasingly stringent health and

environment regulations

• Reduce defective articles during moulding

process
RESPONSE BY ZnO PRODUCERS TO MEETING
RUBBER INDUSTRY NEEDS
Based on “maximization-of-contact” criterion,
have developed:

• Active ZnO (0.1-0.4µm & 30-50m2/g BET)

• Nano-ZnO (20-40nm & 15-45m2/g BET)

 HIGH PURITY ZnO VIA
HYDRO-METALLURGICAL PROCESS (i)

• Developed at METSOL, Adelaide,

Australia

• Conversion of Zinc ores and other Zinc

bearing feed-stocks
 THE METSOL PROCESS
Steel Industry Mining Industry

EAFD Zn Ore
High Purity ZnO Waste
1 Product
3

from Waste Consolidator Concentrator

Disposal
1. EAF Dust Mineral
Concentrates

2. Crude ZnO 2 Zn Smelters

Zn
3. Oxidised
ZnO Producers

Zinc Ores
ZnO
 HIGH PURITY ZnO VIA
HYDRO-METALLURGICAL PROCESS (ii)

ADVANTAGES over conventional “French”

process for ZnO manufacture:
• Lower energy cost
• Relatively low-cost raw material
• Can “tailor-make” range of Surface Area
to suit individual rubber sector needs
 TYPICAL SURFACE AREA
m2/g BET
“French” process ZnO:
2.5m2/g (low) to 12m2/g (high)

METSOL ZnO:
3, 5, 10m2/g current grades
40m2/g being developed
 PARTICLE SIZE & DISTRIBUTION
Particle size distribution of ZnO Grades
100 (Powder form)
90

80

70
Intensity

60

50

40

30

20

10
0 1 2 3 4 5 6 7 8 9 10 11

Diameter (µm)
Control MPP004 MPP005 MPP006
 RHEOLOGICAL BEHAVIOUR
8
7
6
Torque, dNm

5
4
3 ZnO(WS) MPP004

2 MPP005 MPP006
1
0
0 10 20 30 40 50 60
Time,min.
 PHYSICAL PROPERTIES
(TYRE TREAD COMPOUND)
Grade of Zinc oxide
Physical properties
ZnO(FP) METSOL4 METSOL5 METSOL6
Tensile Strength, MPa 28.0 26.2 27.2 25.7
Modulus 100, MPa 0.6 0.6 0.7 0.7
Modulus 300, MPa 1.5 1.6 1.7 1.6
Elongation at Break, % 780 740 730 740
Dunlop Resilience at 23°C, % 88 90 90 90
Tear strength, trouser, kN/m 5.5 4.9 4.8 4.8
Abrasion resistance index, % 24 27 34 29
 PHYSICAL PROPERTIES
(LATEX DIPPED FILMS)
Grades of Zinc Oxide
Physical properties
ZnO (FP) METSOL4 METSOL5 METSOL6

  Natural Rubber (HA) Latex

Tensile Strength, MPa 29.3 27.1 27.8 29.3

Elongation at Break, % 900 865 885 895

  Nitrile (XNBR) Latex

Tensile Strength, MPa 18.9 27.4 26.8 28.4

Elongation at Break, % 548 553 530 543

 ENVIRONMENTAL LAWS &
REGULATIONS – OVERVIEW (i)
• Designed to protect human health and the
environment
• Sets limits on quantity and chemical make-up
of waste streams from manufacturing
processes
• Sets strict criteria on hazardous waste
treatment, transport and storage
 ENVIRONMENTAL LAWS &
REGULATIONS – OVERVIEW (ii)
• Exponential rise of new L&R from the 1970’s
• Essentially 3 Government Related Players
that draw up and define L&R:

Parliament legislate
Administrative Agencies monitor
Courts of Law adjudicate when required
ENVIRONMENTAL LAWS & REGULATIONS
AND THE CHEMICAL ENGINEER (i)

• In many firms, Chemical Engineers are

generally tasked in obtaining permits from the
Department of the Environment (DOE)
• They must be familiar with environmental laws
& regulations that affect operations at their
firm
• Their professional conduct demands that they
are responsible in meeting effluent discharge
standards for their firms
ENVIRONMENTAL LAWS & REGULATIONS
AND THE CHEMICAL ENGINEER (ii)

• Chemical Engineers must take into account

the possibility of existing L&R not being
sufficiently rigorous
• They must be totally aware of legal liability of
violating the L&R for their firms and for
themselves
 TUTORIAL ASSIGNMENT

• Shifting the Focus from End-of-Life

Recycling to Continuous Product
Lifecycles

Sample ref: “call2recycle” Betsy Dorn and

Becky MacWhirter, RSE