w r grace cement additivesgrace.teplomax.kz/grace_en.pdfvalue of cement additives increase in cement...

W R GraceCement AdditivesJanuary, 2011

� Leading specialty chemical and materials company

� Founded in 1854

� 2009 worldwide sales: $2.8 billion

� Approximately 6,000 employees

� Offices in over 40 countries

� Listed on the New York Stock Exchange (GRA)

Grace at a Glance

2January 20, 2012 © 2010 W. R. Grace & Co.

� Member of Fortune 1000

Business Portfolio

2009 Grace Sales by Product Group 2009 Grace Sales by Region


$1.1 billion Europe, Middle East and Africa

$1.0 billion North America

$0.5 billion Asia Pacific

$0.2 billion Latin America

$1.0 billion Grace Davison Refining Technologies

$0.9 billion Grace Construction Products

$0.6 billion Grace Davison Materials Technologies

$0.3 billion Grace Davison Specialty Technologies

Numbers may not total due to rounding

Global Production Network


Operations in Over 40 Countries54 plants provide a global footprint and ensure a global service

Specialty Construction Chemicals(SCC)

Specialty Building Materials(SBM)

� Concrete Admixtures

� # 2 world wide

� WaterproofingSystems

Grace Construction Products

Product Range

5

� Cement Additives

� # 1 world wide

� Masonry Products

� ArchitecturalConcrete

� Fire ProtectionProducts

January 20, 2012 © 2010 W. R. Grace & Co.

� Why use an additive?

� Cement can be made without usingchemical additives

� They are not (usually) needed

� So why do some plants use them?

� How to discover a profitable way to exploit theapplication of a chemical additive?

Why Cement Additives?

6

� Create economic value from the benefitsthat an additive can create that exceedstheir cost

� Requires knowledge of cement plant,cement, market requirements, costs,flexibilities/constraints, etc

� Requires knowledge of cement additivecapabilities, applications, formulations,costs, etc

� Requires a rigorous evaluation procedure


� World Leading supplier to the cementindustry since 1930’s

� Dedicated organization, focused on cement

� Network of laboratories for technical service,R&D and longer term Innovation

� Technical specialists with strong expertise incement production, grinding, cementchemistry, and chemical formulations

Why Grace?

7

y,

� Proven product development andintroduction to the industry

� Rigorous evaluation and application analysiswith established methods and tools

� Global presence & global organization

� Successful sales to more than 500mmtcement


Value of Cement Additives

� Increase in cement mill output, with associated reduction in cementmill system kWh/tonne, reduction in mill run hours and reduction incement grinding costs.

� Increase production capacity to meet sales volume.

� Improving cement flowability (reduce pack-set) to shortenloading/unloading operations and reduce distribution costs.

� Improve cement performance, to meet customer needs, satisfyStandards, meet/exceed competition and improve market position.

8

� Improve cement performance to allow clinker chemistry changes orto lower raw material/fuel costs from use of alternative materials.

� Improve cement performance to increase use of cementitiousmaterials (i.e. non Portland cement clinker).

� Improve cement performance to use cementitious materials to reducethe clinker factor to lower compositional costs, to increase cementvolume per unit of clinker, to reduce environmental impact (e.g. CO2).

� Improve cement performance to permit higher class of cement or newcement type or to meet new market needs.


Cement Additives – Development

Chemical compounds for usein the production of cement toincrease the output andefficiency of the grindingprocess and improve theperformance and quality of thefinished cement, with theobjective to reduce overall

9

manufacturing costs.

9

1967

HEA2® amineacetate grindingaids patented

1970

TDA® QualityImprover seriesintroduced forblended cement

1990

CBA® QualityImproversdeveloped andpatented

2003

ESE® non-chloride earlystrengthenhancersintroduced

2004

SYNCHRO®

chromium-reducingadditivesintroduced


Cement Additives – Traditional Groups� Cement Processing Additives: Grinding Aids

� Improve grinding process efficiency: increase tonnes/hour & reduce specific energy consumption

� Cement Performance Additives: Quality Improvers� significantly improve cement performance and quality

� e.g.: increased strength development, accelerated/delayed setting, reduced water demand, etc.

� allow higher clinker replacement levels

� Cement Functional Additives:� Masonry Cement Additives

Ch i (VI) R d i Additi

10

� Chromium (VI) Reducing Additives


� Reduce coating and Reduce Packset

� Increase Mill Output, by 5 - 30%

� Narrower cement PSD (Increase RRN)

� Increase 28-day strength, 5-15% or say 2 - 10 MPa

Cement Additives – Capabilities

Process

Grinding A

ids

Quality Im

prover

11

y g , y

� Increase 2-day strength, 10-30% or say 2 - 10 MPa

� Reduce setting time, 10-40 minutes (initial set)

� Extend setting time, 10-40 minutes (initial set)

� Reduce water demand (concrete), by 2 - 5%

Quality

Improver


Defining Targets Value Product Proving Closing

OpportunityAssessment

ProcessCement

PerformanceMarket

Additive Target

Grinding SystemCement &

MarketPerformance

Value Created

Energy CostsMaterial costs

ProductionMarket Value

Plant Trial

Industrial TestCustomer PlantShared Results

Agreement

SupplyConditionsService &Support

ProductSelection

ScreenCustomise

DosageCost

Customised Cement Additives Evaluation

12

Defining Targets Value Product Proving Closing

Where can aChemical AdditiveCreate Benefits?

What are theTargets of a

Chemical Additive?

Understandthe Total Value

Customised Solution,Meeting Targets,

Creating Net Economic Benefit

Mutual AssessmentMutual Agreement

Continual AssessmentAnd Improvement


Typical Typical Contribution Cement Grinding Water Setting Compressive StrengthRange Dosage to Cement Cl Flowabil ity, Aid Demand Time 1-3d 28d

g/t g/t g/t Packset

MTDA 150-500 300 0 ** *** = = = =

HEA2 M/K 150-500 300 0 *** *** = (-) ** =

HEA2GL 150-500 300 0 *** *** = = * =

HEA2 SP 150-500 300 0 ** *** = = = =

TDA Z 1000-2500 1500 100-300 *** *** = (-) **** =

Product selection

13

TDA Z 1000 2500 1500 100 300 ( )

TDA J 1000-2500 1500 0-200 *** *** ** = *** */**

TDA S 1000-2500 1500 0-150 *** *** **** =/(+) * =

CBA 1104 150-400 250 0 **** **** = =/(-) */** ****

CBA 1115 300-600 400 0 **** **** = (-) */** ***

CBA 1250 600-1200 800 0 *** **** ** =/(+) */** ***

CBC 1000-2000 1500 100-300 *** *** =/** (-) *** ***

Higher Value Creation

Version 4.3

ReferenceMill Power 4,000 kW Electricity 0.075 Eu/kWh None GA 1 GA 2 QI QI 2Ancillaries 900 kW R&M 0.4 Eu/t Additive Cost/t 0 900 600 1300 2000

Total 4,900 kW Clinker 20 Eu/t Dosage g/t 0 250 250 350 300Clinker tonnes 700,000 SCM 10 Eu/t SCM % 15 15 15 19 24

CO2 0 Eu/t t/hr 110 120 120 122 122Clinker CO2 Factor 862 kg/t kWh/t 44.5 40.8 40.8 40.2 40.2

kWh/t cost 3.34 3.06 3.06 3.01 3.01R&M Cost/t 0.40 0.37 0.37 0.36 0.36

Composition cost/t 1 17.50 17.50 17.50 17.10 16.60

Simplified Value Model Grinding Aid, Low Cost Grinding Aid, Quality Improver, Customized Product


pCO2 cost/t 1 0.00 0.00 0.00 0.00 0.00

Sum 21.24 20.93 20.93 20.47 19.97Saving/t 0.31 0.31 0.77 1.27

Additive Cost/t 0.00 0.23 0.15 0.46 0.60Net Saving/t 0.09 0.16 0.31 0.67

Annual Saving 75,900 141,525 273,838 584,463% Return 39% 108% 69% 111%

Cement Volume 1 875,000 875,000 875,000 921,053 985,915Increase 0 0 0 46,053 110,915

1 Assumes 5% gypsum

GA 1 Traditional grinding aidGA 2 Formulated low cost grinding aidQI Traditional Quality ImproverQI 2 Customized Quality Improver

� Cement additive value assessment andoptimization

� Cement Additive selection

� Cement Additive trials

� Mill Audits

� Problem solving

Technical Support

15

� Mill system

� Cement performance

� Concrete performance

� Concrete admixture issues

� Cement Technology Training


� Usually added directly to the mill or mill feed

� Use permitted by Cement Standards

� Formulated cement additives used since 1930’s

� Usually water based solutions

� Introduced at low levels typically at:

Cement Additives

January 20, 2012 16

� Introduced at low levels, typically at:

� between 0.01% and 0.20% or

� Processing Additives

� Perfomance Additives

� Functional Additives

� Principal application is for an increase in tonnes/hourat constant cement fineness (m2/kg)

� Usually low dosage, typically at:

�between 100 and 500g/t(100 500ppm)

Processing Additives

January 20, 2012 17

(100 - 500ppm)

� Influence on cement qualityis usually small (or not the main intention for

their use)

� The majority are based on alkanolamine andpolyglycol chemistry

� Principal application is for an intended influence oncement performance characteristics

� Usually also provide benefits as a grinding aid

� Usually higher dosage, typically at:

� between 400 and 2000g/t (400 - 2000ppm)

Performance Additives

January 20, 2012 18

� Usually higher cost/tonne of cement (but greaterbenefits)

� Utilise a combination of chemicals, often both organic andinorganic

� Formulated to provide specific benefits

� Can increase SCM and lower CO2

� Intended to provide a new function to the cement

� Can also provide benefits as a grinding aid

� Utilise a combination of chemicals, often both organic andinorganic


Functional Additives

January 20, 2012 19


� Application Examples:

� Masonry Cement

� Air, Board life, Water retention

� Chromium Reduction

� Their main influence is to reduce the effects of inter-particle attractive forces.

� This provides benefits to grinding efficiency via:

�Reduced agglomeration and coating of the mill

Grinding Mechanisms

January 20, 2012 20

gg ginternals

� Improved dispersion of feed to the separator -increased separator efficiency, lower by-pass

�A reduction in the mill filling level

• Rittinger - Linear Relationship between SSA and Energy

• Deviation due to Agglomeration and Coating

• Mechanical Causes - particle packing

Mechanisms of Grinding AidsAgglomeration and Coating

Grinding Mechanisms

January 20, 2012 21

p p g

• Physical Causes - surface charges

• Thermodynamic Causes - surface energy

• Chemical Causes - hydration bridges

• Agglomeration and Dis-Agglomeration

• Coating - compressible layer

Grindability Curves - Rittinger

250

300

350

400

450

500SS

A (m

2 /kg)

Rittinger

A

B

Grinding Mechanisms

January 20, 2012 22

0

50

100

150

200

0 10 20 30 40 50 60 70 80

Mill Only kWh/tonne

Cem

ent S

SA (m

Grind “End-Point”

“Agglomeration”“Straight Line” - Rittinger

Deviation from RittingerAgglomeration/Grinding

Grinding Mechanisms

January 20, 2012 23

• Liners and grinding media

• 1. “None”

• Appearance of “metal” as surface

• 2. “Light”

• Appearance of “cement” as surface

Mill Audit - Chamber 2 Coating

Grinding Mechanisms

January 20, 2012 24

Appearance of cement as surface

• Readily cleaned by hand to reveal “metal” surafce

• 3. “Moderate”

• Appearance of “heavier” cement as surface

• Partially cleaned by hand to reveal “cement/metal” surface

• 4. “Heavy”

• Appearance of “thick” cement as surface

• Difficult to see metal surface, even after cleaning by hand

Influence of Mill Exit Fineness on Ball Mill Efficiency

30

35

m2/

joul

e)

Grinding Mechanisms

January 20, 2012 25

10

15

20

25

50 100 150 200 250 300 350 400 450 500 550

Mill Exit Fineness (m2/kg)

Mill

Effi

cien

cy (c

m2/

joul

e)

No Additive


30

35

m2/

joul

e)

Grinding Mechanisms

January 20, 2012 26

10

15

20

25

50 100 150 200 250 300 350 400 450 500 550


Mill

Effi

cien

cy (c

m2/

joul

e)

No Additive


30

35

2/jo

ule)

Grinding Mechanisms

January 20, 2012 27

10

15

20

25

50 100 150 200 250 300 350 400 450 500 550


Mill

Effi

cien

cy (c

m2/

joul

e)

No Additive

With additive

Increased Grinding Efficiency

Separator PerformanceCoarse Grade Efficiency - Tromp curve

60

70

80

90

100

ency

(%

)

Grinding Mechanisms

January 20, 2012 28

0

10

20

30

40

50

0.1 1 10 100 1000

Particle Size

Coa

rse

Gra

de E

ffici

ency

(%

)

No Additive

Separator PerformanceCoarse Grade Efficiency - Tromp curve

60

70

80

90

100

ency

(%

)

Grinding Mechanisms

January 20, 2012 29

0

10

20

30

40

50

0.1 1 10 100 1000

Particle Size

Coa

rse

Gra

de E

ffici

ency

(%

)

No Additive

With additive(same C. Load)

Reduced By-Pass

Reduced FinesAgglomeration andEntrainment

• Hold-Up = Tonnes of Material Retained in the Mill

• Residence Time = Hold-Up/Total Feed Rate, (RT = W/F)

• Void Filling = Percentage of Media Voids taken by Material

Mill Hold-Up, Residence Time, Void Filling

Grinding Mechanisms

January 20, 2012 30

• Residence Time by Fluorescein Tracing

•Then Hold-Up, (W = RT * F)

•Then Void Filling (From volumes of media and material).

• Void Filling by Mill Internal Inspection

High Void

HeightAbovePowder

HeightAboveCharge

Powder Loading, Void Filling

Grinding Mechanisms

January 20, 2012 31

gFilling

Low VoidFilling

VolumeLoading

MillDiameter

Influence of Powder Filling on Mill efficiency

90

100

110

ncy

(%)

Low Efficiency -High Residence Time

Low Efficiency -High Rate of Breakage

Grinding Mechanisms

January 20, 2012 32

60

70

80

0 20 40 60 80 100 120 140 160 180

Void Filling (%)

Mill

effi

cien

cy (%

)

Optimum Powder Filling at 85% of Voids

High Residence TimeLow Rate of Breakage

High Rate of BreakageLow Residence Time

• Diaphragm Design and Condition• Mill Throughput• Media Sizes• Volume Loading

Factors Influencing Void Filling

Grinding Mechanisms

January 20, 2012 33

• Material Characteristics (fineness, moisture,…)• Separator Type, Efficiency and Circulating Load• Mill speed• Mill Ventilation• Cement Additives (type and dosage)

Influence of Mill Throughput on Void Filling

90

100

110

120

g(%

)

85% Void Filling

110% Void Filling

Grinding Mechanisms

January 20, 2012 34

50

60

70

80

0 50 100 150 200 250 300

Relative Mill Throughput (%)

Void

Fill

ing

(%)

85% Void Filling

Influence of Ball Size on Void Filling

110

120

130

140

g(%

) 110% Void Filling

Grinding Mechanisms

January 20, 2012 35

60

70

80

90

100

1 10 100

Mean Ball Size (mm)

Void

Fill

ing

(%)

15mm 40mm

85% Void Filling

• Increased dry flowability

• Reduced Mill Residence Time

• Reduced Mill Hold-Up

Mechanisms of Grinding Aids

Grinding Mechanisms

January 20, 2012 36

• Reduced Void Filling

• Reduction Typically 10-40%

• Can represent 10% gain in efficiency

Influence of Powder Filling on Mill efficiency

90

100

110

y(%

)

Typical Mill Operationat >100% (2nd Chamber)For optimisedCirculating Load

Cement AdditivesReduce Void Filling

Grinding Mechanisms

January 20, 2012 37

60

70

80

90

0 20 40 60 80 100 120 140 160 180

Void Filling (%)

Mill

effi

cien

cy (%

)

Optimum Powder Filling at 85% of Voids

Reduce Void Fillingand IncreaseMill Efficiency

Low Void Filling =Low Efficiency -High Rate of BreakageLow Residence Time

High Void Filling =Low Efficiency -High Residence TimeLow Rate of Breakage

� Grinding Efficiency can be 0-30% higher

� Reduced agglomeration and coating of the mill internals

� Can be up to 10% benefit

� More important at high fineness (and can be more than 10%)

� Improved dispersion of feed to the separator, leading to increasedseparator efficiency, lower by-pass

Grinding Mechanisms - Summary

January 20, 2012 38

� Can be up to 5% of benefit

� More important in older separators

� A reduction in the mill filling level

� Can be up to and more than 10% benefit

� BUT can be a negative effect

� More important in mills with high void filling

"Coating"Heavy Moderate Light/None

Void Filling

>1.10 ***** **** ***

Effectiveness of Grinding Additives forIncreased Grinding Efficiency

39

0.90 - 1.10 **** *** **

<0.90 *** ** *

Key: ***************

Excellent Effectiveness

Very Good Effectiveness

Good Effectiveness

Moderate Effectiveness

Minimal Effectiveness

Note: Effectiveness of grinding additives refers to grinding efficiency only, i.e. mill output and kWh/t,

not to effectiveness of enhancing cement performance.

•Results in less finesreturned to the bed.

•Improves dispersionin the separator

Vertical Mills - Influence of Cement Additives•Vertical Roller Mill

Coarser materialback to table

Fines toseparator

40

Oversize to scraper channel

Dam Ring

40 - 60 m/s

Assists the de-aerationprocess in front of the roll.

•Faster compactionspeed

•Less vibrationImproves dispersion

at the nozzle ring

w r grace cement additivesgrace.teplomax.kz/grace_en.pdfvalue of cement additives increase in cement...

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