Final presentation compiled v12

NOVEL WASTE
MINIMIZATION FOR STEEL
MANUFACTURING
N O V E M B E R 2 7 TH, 2 0 1 2

Adriano Arnini , Amir Fakhruddin Mohamed,
Anika Mohammed, Francis Bui,
Xiaobo Pan, Sonia Liscio

OVERVIEW

1. Integrated Steel Mill Waste Management Plan
2. Glacius’ Proposal
3. Key Unit: Reactor
4. Settling and Storage Sites
5. Economics
6. Recommendations & Conclusions

1.Steel Mill Waste Management
1 2.Glacius’ Proposal 3.Key Unit: Reactor
4.Settling & Storage 5.Economics
6. Recommendations &Conclusions

INTEGRATED STEEL MILL
WASTE MANAGEMENT PLAN
 US Steel Canada
 Steel-making Process

2

Objectives

1. Maximize the amount of waste utilized from
an integrated steel mill

2. Reduce the costs associated with waste
management

1.Background 2.Process Description
3
3.Reactor 4.Equipment 5.Hazards
6.Economics 7.Conclusions

US Steel Canada – Hamilton Works Plant

Formerly Stelco Inc.
Lake Ontario
Hamilton Harbor

Site chosen to
Hamilton Works
demonstrate concept

Steel production
capacity:
Google. (2012). Google Maps. Retrieved November 20,
2.6 Million tonnes/year 2012, from https://maps.google.ca/)

4

Integrated Steel Mill Recycled
O2 Limestone Steel

Iron ore Pig Iron Molten Steel
Basic Oxygen
Coke
Blast
or Electric Arc
Furnace
Limestone Furnace

Blast Furnace Slag Steel Slag

Species Composition [%wt] Species Composition [%wt]
SiO2 35 SiO2 15
CaO 33 CaO 45
Al2O3 20 Al2O3 2
MgO 7 MgO 10
MnO 1 MnO 4
Fe2O3 1 Fe2O3 22
SO3 2
Trace Metals 1 Trace Metals 2

5

Integrated Steel Mill Regeneration
 HCl(aq) recycle
 Costs $150/tonne WPL
Molten Steel
Finishing Pickle Liquor  Energy intensive
Pickle Liquor
Processes (30% HCl(aq))
 Acid bath
 Refining  Strip
Regeneration iron oxide layer
 Casting from steel surface
 Rolling Waste Pickle
Liquor

Species Composition [%wt]
H2O 67
Steel HCl 10
Products FeCl2 20
Trace Metals 3

6

The Proposal

Utilize two major waste streams from the steel mill
to make a significant value added product

Waste Streams: Product:
De-icing Fluid
Steel Slag Waste Pickle
Liquor

Source: Source:
http://www.betweenthelake http://www.environmentallever Source:
s.com/iron/fobf_7_5_03.ht age.com/industry/steel/Steel.h http://www.mto.gov.on.ca/english/transtek/roadtalk/r
m tml t16-4/index.shtml

7

Background

Stelco Inc. initially proposes idea

Preliminary lab studies conducted
 Results show idea is feasible
 Revealed no major environmental concerns

US Steel Corp. purchases Stelco Inc.
 Project suspended indefinitely

8

GLACIUS’ PROPOSAL
 Design Philosophy
 Process Schedule
 Background Chemistry
 Product Specifications

9

Design Philosophy

Simplicity
 Ease of operation

Economic Return
 Minimize capital and operating costs

Novel and Innovative
 Patent and license opportunity
 Ability to implement globally

10

De-icing Fluid Production Schedule
Basic Oxygen
Finishing Process Furnace

Waste Pickle
De-icing Fluid Liquor
Steel Slag

Solids to Steel
Mill Sediment Set 1 Reactors Set 2

Sediment Pond
Solids to Steel
Mill

Reservoir

11

Main Chemical Reactions
Steel Slag De-icing Fluid Water
Waste Pickle Liquor
1. CaO(s) + 2HCl(aq)  CaCl2(aq)+ H2O(l)
∆H = - 190kJ/mol
∆T =
2. 20oC
MgO(s) + 2HCl(aq)  MgCl2(aq) + H2O(l)
∆H = -150kJ/mol
By-Product

3. CaO(s) + FeCl2(aq)  CaCl2(aq) + FeO(s)
∆H = -720kJ/mol

12

Reaction Data Assumptions

Limited Access to Preliminary Research
 Pilot studies required

Literature for Similar Reaction
 Ideal batch reactor
 0 to 31 Hours reaction
 Less than 10mm particle size

Buffer time allotted
 Varying particle size
oUp to 35mm

13

Product Quality

Minimize amount of heavy metals
 pH = 9.5
 Control with neat HCl

Retrieved from Dyer, J. A., Scrivner, N. C. and Dentel, S. K. (1998), A practical guide for determining the
solubility of metal hydroxides and oxides in water. Environ. Prog., 17: 1–8. doi: 10.1002/ep.670170112

14

Final Product Specifications (De-icing Fluid)

MgCl2 Trace
Trace Metals 6% Metals,
CaCl2 0.003%
(ppm) 24% H2O
FeCl2 390 70%
Fe(OH)2 0.80
Ca(OH)2 390
Mg(OH)2 40
Cr(OH)3 0.02
Ni(OH)2 0.00017
Cd(OH)2 0.11
Pb(OH)2 1.5

15

By-Product Specifications (Sediment)
Trace Trace (wt%)
Cr 10%
5% Fe Mn 0.04
Si 58% Al 0.020
14% Ni 0.03
Ti 0.009
S 9.0 E-04
Mg P 4.6 E-03
3% CN- 1.2 E-05
Ca As 1.5 E-05
10% Pb 0.004

Trace Metals
(ppm)
Forest Soil Cd <1
Cr 22
Compariso Ni 15
n Source: Pb 28
Bavrlic, K., & Quenselle, P.
(2010). Monitoring Forest Integrity
within the Credit River Watershed.
16 Meadowvale.

KEY UNIT: REACTOR
 Design
 Recirculation System
 Internal Design
 External Design

17

Plant Layout
WPL
Back-Up
Tanks
Reservoi
Reactors r
Loading
Area
HCL
Storag
e Shed

Main
Reservoi
r

Sedimen
t Pond

18

Reactor Design

Batch reactor 2.0 m 1.0 m 2.0 m

Sloped walls
2.0 m

Capacity = 110m3
2.0 m
0.3 m
Dimensions
 L = 7m
 W = 5m

19

3-D Reactor Layout

20

Recirculation Process

Benefits
 Increased mixing effect
Unites States Patent Office. (1976). Patent #3958952.
(Original work published 1974). Retrieved from
oResulting solution is
http://www.google.com/patents/US3958952?printsec=dra
wing#v=onepage&q&f=false

denser than solvent
 Avoid clogging of the
plate with fines
Top View
 Less movement of slag
reduces wear on lining

21

Stop Logs

Stacked
Removable
Manual or Automatic

Stop Logs vs. Pumps
 Gravity vs. electricity
oHorsepower is 6hp
http://www.internationalwastewater
oMinimal energy .com/Products/Gates.aspx
oMinimize operating cost

22

SETTLING & STORAGE SITES
 Sediment Pond
 Reservoirs
 Covering Structure

23

Sediment Pond

Sediment
Pond

24

Sediment Pond

Purpose
 To settle the solids

Material
 Carbon steel lined
with Reinforced
Polypropylene

Dimensions
 40m x 14m x 5m

Capacity
 2800m3

25

Settling Rate & Drainage Time

Settling rate Drainage Time
 The settling rate is  1 stop log = 7 minutes
0.1m/h
 All solids will settle in
one week

26

Reservoirs

Backup
Reservoir

Main
Reservoir

27

Main Reservoir

Purpose
 To store
deicing fluid

Dimensions
 51m x 60m x 3m

Capacity
 9200m3

28

Backup Reservoir

Purpose
 When reservoir is full
& for maintenance
 To store extra
production

Dimensions
 28m x 28m x 3m

Capacity
 2400m3

29

Materials of Reservoirs

Body Lining
1. Vegetation 1. Reinforced
2. Fill Dirt polypropylene sheets
3. Steel Slag 2. Calcium bentonite clay

Vegetation
Fill Dirt
Slag
RPP
Clay

30

Covering Structure

Purpose Covering Structure
 To cover product
from rain

Dimension
 125m x 155m

Area
 19400m2

31

Hazard Mitigation
WPL
Tanks

Reactors

HCL
Storage
Shed

32

ECONOMICS
 Comparison Between Existing and Proposed Plan
 Cash Flow and Sensitivity Analysis
 Current Market of De-icing Agents
 Cost-saving Benefits

33

Replacing Regeneration Process

De-Icing Fluid Production: 11,000 tonnes per year
De-Icing Fluid Unit Price: $300 per tonne
Proposed Plan Current Process
Revenue from De- $3,300,000 Regeneration of ($15,800,000)
icing Fluid Waste Pickle Liquor

Cost of Neat Pickle ($16,800,000)
Liquor
Total Cost $13,500,000 Total Cost $15,800,000

Net Benefit: $2,300,000

34

Cash Flow Analysis

 Total capital investment: $8.6M  Payback period: 6 years
 Annual operating cost:  Net present value: $24.7M
$727,000
 Annual earnings before tax and
interest: $2.73M
$4,000,000.00

$2,000,000.00

$-
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
$(2,000,000.00)

$(4,000,000.00)

$(6,000,000.00)

$(8,000,000.00)

$(10,000,000.00)

35

Sensitivity of Project
Internal Rate of Return vs.
60
Variation of Factors
Internal Rate of Return (IRR) in %
50

40 Total Capital
Investment

Revenue
30

Maintenance
20

MARR
10

0
-50 -40 -30 -20 -10 0 10 20 30 40 50

Variation in %

36

Current Market for De-icing Agents

Ontario usage
 500,000 to 600,000
tonnes of salt per year

De-icing trucks
 City of Hamilton already
purchasing new liquid
application trucks
Fixed Automated Spray Technology. (n.d.). Retrieved November 18, 2012, from
http://www.ibigroup.com/Pages/Project.aspx?ProjectId=430&DisciplineId=3&PracticeId=50&pageNam
Infrastructure in place e=AreaOfPractice.aspx&backString=AreaOfPractice.aspxxDisciplineID=3ppracticeID=50ppage=

 Fixed Automated Spray
Technology (F.A.S.T)

37

City of Hamilton – Cost of Materials

Road salt De-icing fluid
 Unit price: $50 per tonne  Unit Price: $300 per tonne
 Annual Usage:  Annual Usage:
26,000 tonnes per year 2,730 tonnes per year
 Total cost: $1,300,000  Total cost: $830,000

Savings of $470,000

38

Cost Savings & Benefits

Environmentally friendly material
 Zero release of ferrocyanide
 Introduction of calcium ions in soil

Corrosion reduction
 Reduced chloride release

Socioeconomic benefits
 Vehicular accident reduction (F.A.S.T)

39

RECOMMENDATIONS &
CONCLUSIONS
 Market Expansion
 International Implementation
 Paramagnetic Iron Oxide Recovery

40

Recommendations
Market Expansion
 Scale-up production
 Solid product

Global Implementation
 Minimizing footprint
 Top steel producers & calcium chloride consumers
 Alternate uses for calcium chloride solution

Alternate Use for Sediment
 Paramagnetic iron oxide recovery Magnetite
 Potential source of greater revenue

41

Conclusions

Maximized amount of waste used

Converted to a marketable product

Cost savings of $2,300,000/year

Novel, simple, energy-efficient

Adaptable to steel mills world-wide

42

Acknowledgements

Henry Miyamoto
Jill Lam
Donald Kirk
Graeme Norval
Rosanna Kronfli
Lydia Wilkinson

43

Overview Back-up Slides

Slide 58

45

Reactor Dimensions with Reactant Levels

46

Mass Balance

Per Set of 2 Batch Reactors (Weekly basis)

47

pH Control

Reactors
A
E
Turn off
AES
L
Turn on
AESH

HCl
Tote

Metering
Pump

49

Loading Reactor – P&ID

52

Time to Drain Calculation

53

Settling Time Calculation

54

Reactor Flow rate & Pump Required

55

Solubility of Heavy Metals

Retrieved from Dyer, J. A., Scrivner, N. C. and Dentel, S. K. (1998), A practical guide for determining the solubility of metal
hydroxides and oxides in water. Environ. Prog., 17: 1–8. doi: 10.1002/ep.670170112

56

Production Schedule
Reactor Sediment Reservoir
Pond
• 1 Week • 1 Week • 10 000
of Mixing of tonnes
• Recirculation Settling produced
process • Sediment
• 1 Week removed
during
of maintenance
Settling
• Vacuum
Pumped

2 Batch Reactors per week
Staggered Production
 4 Reactors in total

57

HCl Price

 Current price of HCl $250
 Maximum HCl price when regeneration process
becomes preferred: $284

58

Vacuum Truck

Datasheet
3000 gallons (us), Stainless tank, D.O.T. 407/412
6400 cfm, 27'' Hg., high vacuum pump

Source: http://www.supervac2000.com/en/specialized-
trucks/vacuum-truck/svpt-6400-tc-and-dot-coded-tank-
29.html
59

Total Capital Investment

A. Direct Cost
1. Equipment $ 2,415,834.91
2. Instrumentation and Controls $ 238,989.58
3. Electrical Installations $ 183,838.14
4. Building Including Services $ 128,686.70
5. Yard Improvements $ 367,676.28
6.Service Facilities $ 367,676.28
B. Indirect Cost
1. Engineering and Supervision $ 551,514.42
2. Construction Cost $ 1,295,945.66
3. Contingencies $ 888,648.45
4. Startup Expense $ 999,729.51
C. Working Capital $ 1,190,166.39

60

Plant Initial Investment Detailed Spreadsheet 1/2
A. Direct Cost
1. Equipment Unit Cost Quantity Unit Installation Total Unit Cost
HCl Units
Semi Bulk Tanks/Totes $ 455.00 12 tote $ 5,460.00
Metering Pump $ 3,485.00 2 per pump $ 1,394.00 $ 9,758.00
Spill Skid $ 765.50 2 per skid $ 1,531.00
Waste Pickle Liquor Units
Low Carbon Steel Tanks $ 67,400.00 3 per tank $ 30,330.00 $ 293,190.00
HDPE Liner $ 7.00 435 per m2 $ 0.33 $ 3,188.55
Centrifugal Pump $ 28,200.00 4 per pump $ 11,280.00 $ 157,920.00
Concrete Berm $ 260,000.00 1 per berm $ 260,000.00
Reactor Units
Low Carbon Steel Tanks $ 53,900.00 4 per tank $ 24,255.00 $ 312,620.00
HDPE Liner $ 7.00 516 per m2 $ 1.33 $ 4,298.28
Double Piston Diaphragm Pump $ 89,300.00 5 per pump $ 35,720.00 $ 625,100.00
Settling Pond Unit
Reinforced Polypropylene Liner $ 10.00 1100 per m2 $ 0.38 $ 11,418.00
Low Carbon Steel Body $ 304,200.00 1 per body $ 136,890.00 $ 441,090.00
Conveyor Belt $ 118,200.00 1 per belt $ 118,200.00
Reservoir Units
Calcium Bentonite $ 300.00 25 per tonne $ 7,500.00
Reinforced Polypropylene Liner $ 10.00 4950 per m2 $ 0.38 $ 51,381.00
Sump Pump $ 20,500.00 1 per pump $ 8,200.00 $ 28,700.00
Auxiliary Units
Pipe $ 36.88 330 per feet $ 16.60 $ 17,647.08
Level Indicator Controller $ 1,450.00 7 per controller $ 10,150.00
pH Controller $ 1,500.00 4 per controller $ 6,000.00
Pressure Indicator Controller $ 1,694.00 4 per controller $ 6,776.00
HDPE Pipe Reducer $ 18.00 4 per reducer $ 72.00
Check Valves $ 300.00 1 per valve $ 300.00
Butterfly Valves $ 750.00 18 per valve $ 13,500.00
3-way Valve $ 600.00 1 per valve $ 600.00
Magmeter $ 1,455.00 1 per magmeter $ 1,455.00
Flow Control Valve $ 420.00 1 per valve $ 420.00
Filter $ 560.00 22 per filter $ 420.00 $ 21,560.00
Solenoid Valves $ 2,000.00 3 per valve $ 6,000.00
Purchased Equipment Subtotal $ 1,838,381.40 $ 2,415,834.91

61

2. Instrumentation and Controls
Normal Solid-fuild Chemical Processing 13% of Purchased-equipment $ 238,989.58 $ 238,989.58

3. Electrical Installations
Electrical-installations cost 10% of Purchased-equipment $ 183,838.14 $ 183,838.14

4. Building Including Services
Solid-fuild Expansion at an existing site 7% Purchased-equipment $ 128,686.70 $ 128,686.70

5. Yard Improvements
Approximates 20% of Purchased-equipment $ 367,676.28 $ 367,676.28

6.Service Facilities
Approximates 20% of Purchased-equipment $ 367,676.28 $ 367,676.28

Subtotal $ 3,702,701.89
Plant Initial Investment Detailed Spreadsheet 1/2
B. Indirect Cost Cost Total Cost
1. Engineering and Supervision
Approximates 30% purchased-equipment $ 551,514.42 $ 551,514.42

2. Construction Cost
Contractor's Fee 5% $ 185,135.09 $ 185,135.09
Construction 10% of fixed capital $ 1,110,810.57 $ 1,110,810.57

3. Contingencies
Approximates 8% of fixed capital $ 888,648.45 $ 888,648.45

4. Startup Expense
Approximates 9% of fixed capital $ 999,729.51 $ 999,729.51

Subtotal $ 3,735,838.05

C. Fixed Capital Investment $ 7,438,539.94

D. Working Capital (10-20% of Total Capital Investment) $ 1,190,166.39

E. Total Capital Investment $ 8,628,706.33

62

Production Annual Cost
Total Production Cost
Detailed Plant Annual Operating Cost Spreadsheet
A. Manufacturing Cost
Direct Production Cost Quantity Unit Unit Cost Total Cost
1. Raw Materials
HCl 12 totes/year $ 455.00 $ 5,460.00
Waste Pickle Liquor
Steel Slag
2. Operating Labor 2 operator/year $ 56,600.00 $ 113,200.00

3. Utilities
Electricity 46250 kW-hr/year $ 0.08 $ 3,700.00
Fuel - Petro 17500 liter/year $ 1.30 $ 22,750.00
4. Maintenance and Repairs
0.05 of FCI $ 371,927.00
5. Operating Supplies
0.15 of Main&Rep $ 55,789.05
6. Laboratory Charges
0.15 of Op&Labor $ 16,980.00

Direct Production Cost $ 589,806.05

Fixed Costs
Insurance
0.007 of FCI $ 52,069.78
Plant-overhead costs
0.6 of Op&Labor $ 67,920.00

Manufactuing Cost Total $ 709,795.83

B. General Expenses
Administrative costs
0.15 of Op&Labor $ 16,980.00

Total Product Cost $ 726,775.83

63

Top Steel Producers vs.
Top Calcium Chloride Consumers

Country Steel Production
[million tons]
China 626.7
Japan 109.6
United States 80.5
India 68.3
Russia 66.9
South Korea 58.4
Germany 43.8
Source: Badkar, M. (2011, July 26). The
10 Biggest Steel Producing Countries In Source: IHS Chemical. (2012). Calcium
The World. Retrieved from Business Chloride. Retrieved November
Insider: 2012, from IHS Chemical Web Site:
http://www.businessinsider.com/countrie http://www.ihs.com/products/chemical/pl
s-that-produce-the-most-steel-2011- anning/ceh/calcium-chloride.aspx
7?op=1

64

Alternate Uses Of Calcium Chloride Solution

Source: http://www.calciumchloride.com/market.shtml

65

Paramagnetic Iron Oxide Recovery

Magnetite
• 3 Fe(OH)2 → Fe3O4 + 2 H2O + H2
Separation
• Wet low intensity magnetic separators
Source:
http://www1.southafricacrusher.com/optional
Potential Iron in Solid Waste: 2,300 tonne/year -equipment/low-intensity-magnetic-
separator.php
Alternative Price Revenue
($/tonne) ($/ year)
Magnetic Iron Oxide Recovery $320 $736,000
Sintering Plant $120 $276,000

Difference $200 $460,000
Source: (Iron Ore: Market Outlook to 2020, 7th edition 2012, 2012)

66

Material Selection Process

Corrosion Mechanical Economic
Resistance Reliability Viability

67

Process Equipment Materials
Equipment Body Lining Advantages
Reactor A242 Steel HDPE -A242 highly resistant to
atmospheric corrosion
(Brockenbrough, 2006)
- HDPE chemically inert to
reactants & products and
highly resistant to wear;
widely used with abrasive
slurries (Gabriel, 2001)
Settling Pond A242 Steel Reinforced PP -RPP highly resistant to UV
exposure (Western
Environmental Liner, 2009)
Reservoir 1st layer : Steel Slag 1st layer : Reinforced PP -RPP resistant to UV
2nd layer: Fill Dirt Lining Sheets exposure
3rd layer: 2 nd layer: Calcium bentonite - Clay is a self-healing pond
Vegetation clay sealant to provide extra
safety against leaks (Moine-
Ledoux, 2000)
Stop logs Carbon Steel HDPE -HDPE lining chemically inert
- With EPDM seals and epoxy to reactants & products
painted steel guides -EPDM weathering, UV and
chemically resistant (Rubber-
Cal, 1999)
-Epoxy paint protects steel
from corrosion by chloride
ions

68

Secondary Equipment Materials
Piping Body Lining Advantages
WPL A242 Steel HDPE -A242 highly resistant to atmospheric corrosion
HCl -HDPE chemically inert to reactants & products and
Recirculation highly resistant to wear; widely used with abrasive
De-icing fluid slurries
Flush (Water)
Piping

Pumps Body Lining Advantages
Diaphragm Carbon Natural -Steel provides structural strength
(Recirculation) Steel Rubber -Natural Rubber excellent resistance to severe
Centrifugal abrasion, chemically resistant and low cost (Soft
Metering Natural Rubber, 2012)
Sump

Valves Body Lining Advantages
Butterfly PVC EPDM -PVC is low cost and mechanically strong (Curbell
Solenoid Plastics, 2012)
Check -EPDM provides chemically and UV resistant seal
Flow Control
3-way

69

Equipment Sizing
Table 13: Process Equipment Sizing 1 of 2

Product Mass Density Actual % Volume Design Width Depth Height Comments Stop Logs
[kg] [kg/m3] Volume Volume [m] [m] [m] [m]
[m3] [m3]

Reactor WPL 107000 1450 74.3 0.74
(1 unit) HCl 378 1490 0.25 0.00 Holds half a 7x0.3048
Water 0.00 1000 0.00 0.00 batch of raw 3x0.1524
materials
Slag 37000 3750 9.88 0.10
Total 84.4 100 5 6.875 4

Settling Liquid 4210000 1380 304 0.11
Pond Holds 1 yr solids 14x 0.3048
Solids 3990000 2020 1980 0.72 + 2 liquid 4x0.1524
batches

Total 2280 2740 40 13.9 5

Reservoi Liquid 10500000 1380 7600 0.83
r Holds 1 yr of
Solids 0.00 0.00 0.00 0.00 product -

Total 7600 9120 60 51 3

70

Equipment Sizing Continued
Table 14: Process Equipment Sizing 2 of 2

HCl Supply Mass Balance Vol. with OD [m3] Dimensions [m] of Design Vol. [m3] Comments
Vol. [m3] OD

Radius= 0.5 &Height
0.51 0.61 =1 Holds 2 batches

455.69 535 (Total) - - Holds 3 weeks of WPL

Radius = 3 & Height
WPL Supply - 178 (1/3 of Total) =7 198 Holds 1 week of WPL

Back-Up
Reservoir - 9120/4 = 2280 28 x 28 x 3 2352 Holds ¼ of main reservoir

71

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