Alternatives to Chlorinated Solvents in

Asphalt Testing

Glenn R Webber glennwebber@kersolinc.com

With special focus on Tech Kleen ®* N Propyl Bromide solvents for extractions and recoveries.

416-923-9120

The technical assistance of Andrew Pahalan of Lafarge and John Emery of the JEGEL Group is much appreciated.

Alternatives to Alternatives to Trichloroethylene in Asphalt Trichloroethylene in Asphalt Testing Testing

Ignition Ovens – wider use of ignition ovens are anticipated with the continuing technical activities of asphalt producer user groups.

Alternatives to Trichloroethylene Alternatives to Trichloroethylene in Asphalt Testing in Asphalt Testing

Extraction Solvents D Limonene Based Extraction

SolventsD Limonene based products require a number of

water rinses and drying. Also a wastewater issue identified by Lafarge.

N Propyl Bromide Extraction Solvents (NPB)

N Propyl Bromide works similar to trichloroethylene.

Essentially a drop in replacement.

So why Change from So why Change from Trichloroethylene?Trichloroethylene?

Workplace Environmental Health and Safety.

ODS and Global Warming issues

Environment Canada is moving to reduce Trichloroethylene usage in the workplace

Changes in Canada Effecting Changes in Canada Effecting Degreasing ChemistryDegreasing Chemistry

In 1993, Trichloroethylene (TCE) and Tetrachloroethylene (PERC) were assessed as toxic under CEPA 1988.

In 1994, an Issue Table was convened under the Strategic Options Process to make recommendations on options for reducing the release of these toxic substances. The Issue Table was comprised of representatives of the provincial and federal governments, environmental non-governmental organizations, and industry. The Strategic Options Report of stakeholders’ consultations was released in 1996.

Reference : www.ec.gc.ca/nopp/degrease/en/index.cfm

CEPA- Canadian Environmental Protection Act

Changes in Canada Effecting Changes in Canada Effecting Degreasing ChemistryDegreasing Chemistry

In February 1997, the federal Minister of the Environment announced that regulations would be developed under CEPA, as recommended in the Report, to reduce total Canadian consumption of TCE and PERC used in solvent degreasing operations.

On July 5, 2001, Environment Canada conducted a one-day information session on the proposed regulations. In exploring the issues of content, design and implementation, the views and concerns from stakeholders were noted and reported.

Reference : www.ec.gc.ca/nopp/degrease/en/index.cfm

Changes in Canada Effecting Changes in Canada Effecting Degreasing ChemistryDegreasing Chemistry The solvent degreasing regulations will implement a

freeze in consumption of TCE and PERC for three years, followed by a 65% reduction in consumption for the following years. The regulations will apply to persons involved in degreasing operations (vapor and cold degreasing) who use more than 1000 kilograms of these solvents during a calendar year. An allowance system will set limits on the quantities of TCE and PERC that could be used each year, based on historical uses of these substances by the users. Allowance holders will be able to retire their allowance or to transfer it to other users. Sellers and users of TCE and PERC will be required to submit annual reports to Environment Canada.

The regulations were published in Part II of the Canada Gazette August 13, 2003.

Reference : www.ec.gc.ca/nopp/degrease/en/index.cfm

Changes in Canada Effecting Changes in Canada Effecting Degreasing ChemistryDegreasing Chemistry

For information purposes a compilation of references and links to solvent alternatives and degreasing technologies is available on this web site.

For further information, please contact:Solvent Degreasing CoordinatorTel.: 1-866-944-9944Fax: (819) 994-5030e-mail: tce@ec.gc.ca

Reference : www.ec.gc.ca/nopp/degrease/en/index.cfm

What it means for What it means for Trichloroethylene users in Trichloroethylene users in Canada Canada

All Trichloroethylene sales are tracked and reported to Environment Canada.

2007 a 65% reduction was implemented for users of Trichloroethylene for vapor degreasing in excess of 1000 kilograms.

Reference : www.ec.gc.ca/nopp/degrease/en/index.cfm

Effect of Environment Canada’s Effect of Environment Canada’s Reg.’s on Asphalt LabsReg.’s on Asphalt Labs

In 2007 I was told verbally that EC had an exemption for laboratories that used Trichloroethylene in centrifugal extractors.

EC’s intent was to re-examine this exemption at a later date.

Laboratories using Trichloroethylene for asphalt extractions should consider evaluating alternatives like Tech Kleen AZE Stabilized NPB prior to forced cut backs.

CTAA and the various asphalt associations should play a role in getting NPB approved by the various ministries.

Improved Health and Safety Improved toxicityNo Flash PointHigh solvency power excellent cleanerLow boiling pointLeave zero residuesLow global warming Not regulated by

Montreal ProtocolDrop in replacement for chlorinated solventsRecyclableNo extra steps or water rinsing.

Trichloroethylene Replacement Solvent Characteristics

Solvent ComparisonsSolvent Comparisons Vapor

Boiling Point Density Flash Point

Trichloroethylene 87°C 1.46 none

1.1.1. Trichloroethane 74°C 1.32 none

Methylene Chloride 40°C 1.32 none

Perchloroethylene 121°C 1.62 none

NPB 70°C 1.32 none

D Limonene 176°C 0.844 46-48°C

KB VALUE or CLEANING KB VALUE or CLEANING POWERPOWER

29

56

68

90 94

126124

130 136

0

20

40

60

80

100

120

140

KB Value

White spiritHCFC 141bd-LimonenePerchloroethyleneXyleneNPBTrichloroethaneTrichloroethyleneMethylene chloride

The maximum possible KB (Kauri-Butanol) value, is a solvency power of 140

EVAPORATION RATEEVAPORATION RATE

1.64

0.96

1

0.57

0.18

0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8

METHYLENE CHLORIDE

NPB

1.1.1TRICHLOROETHANE

TRICHLOROETHYLENE

PERCHLOROETHYLENE

The evaporation rate is taken as free standing in air and compared to butyl acetate = 1.

GWP GLOBAL WARMING GWP GLOBAL WARMING POTENTIALPOTENTIAL

0.10.53

0.679

90110

480530

630

0 100 200 300 400 500 600 700

NPBPerchloroethyleneTrichloroethylene

Methylene chlorideHFE 7200111 TCA

HFE 7100HCFC 225bHCFC 141b

Global warming potentials are based on 100 yr horizons

NOT A HAP NOT A HAP (Hazardous Air (Hazardous Air Pollutant)Pollutant)No reporting under NESHAP or

SARA TITLE V LBS USED PER MONTH

US reporting requirements for Trichloroethylene have encouraged the switch to NPB for vapor degreasing.

ATMOSPHERIC LIFETIMEATMOSPHERIC LIFETIME

CFC`s - general 100 Years1.1.1. Trichloroethane 6.5 YearsMethylene Chloride 6 MonthsPerchloroethylene 84 DaysTrichloroethylene 42 DaysNPB 11 Days

N Propyl Bromide N Propyl Bromide SummarySummary SNAP (Significant New Alternatives Policy) Approved by US EPA

under section 612 of clean air act for solvent cleaning applications. NPB is not a HAP and is reportable by NESHAP Contains no chlorine High solvency - excellent cleaner. No residue No Flash Point

DROP-IN REPLACEMENTa. No capital equipment investmentb. No change in process

TCE consumption must be reduced in Canada

Min DOT Approval of NPB Min DOT Approval of NPB 1852 QUANTITATIVE EXTRACTION OF BITUMINOUS MIXTURES

(CENTRIFUGE)

AASHTO T 164, METHOD A (MN/DOT Modified)

1852.1 SCOPE

This method of analysis quantitatively determines the asphalt content of bituminous mixtures using a centrifuge extractor and trichloroethylene or other approved solvents. The use of alternatives like n-propyl bromide and d-limonene, are suitable replacements. These solvents are generally non carcinogenic and essentially non-toxic. Required alterations to this procedure for using n-propyl bromide and d-limonene are covered in the numbered "Notes" below. This method is Mn/DOT's preferred method.

NOTE 1: This procedure differs from AASHTO T 164 as follows: Mn/Dot allows the use of n propyl bromide and d-limonene. When using d-limonene a number of water rinses are required and then the sample is dried at 176.7 ± 5 °C (350 ± 9 °F). MN/DOT also requires the use of Celite (diatomaceous earth) to be added to the mixture. (When using Celite determining the amount of fines in the extract is not required by MN/DOT.) MN/DOT allows a minimum solvent soak time of 1 hour but the extraction process must be completed within 24hrs.

Connecticut DOT Approval Connecticut DOT Approval

“The sample of Tech Kleen STNPB that you submitted December 1, 2007 has been evaluated.

This product has been approved for recommended use as a solvent for extractions with no dilution rate.”

Georgia DOT Approval Georgia DOT Approval

“The Non Chlorinated Asphalt Extraction sample you submitted for an Initial Product Evaluation for Qualified Products List 67 has met all necessary specifications and testing requirements and is approved for use on Georgia Department of Transportation (DOT) projects.”

“Tech Kleen NPB”

Other Approvals Other Approvals

Pennsylvania DOT

Lafarge Canada

n-Bromide Trichloroethylene n-Bromide Trichloroethylene n-Bromide Trichloroethylene n-Bromide Trichloroethylene

19.0mm 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.012.5mm 93.2 93.2 91.4 92.2 93.2 94.2 95.2 93.4 92.49.5mm 74.7 75.4 74.1 74.8 75.2 76.0 74.1 75.0 73.34.75mm 54.6 56.3 54.8 54.9 55.1 54.5 53.2 52.2 53.42.36mm 35.4 37.0 35.1 34.8 35.9 36.4 34.9 34.8 34.21.18mm 25.0 25.2 24.9 24.4 24.6 26.0 24.0 25.5 25.1600um 17.5 17.8 17.2 17.2 17.9 17.3 17.8 17.2 17.5300um 9.4 9.7 9.6 9.1 9.5 9.2 9.7 9.0 9.1150um 5.4 5.5 5.4 5.2 5.4 5.6 5.4 5.3 5.675um 3.6 3.7 3.6 3.5 3.6 3.6 3.6 3.4 3.5% AC 5.00 4.99 5.01 5.08 5.02 4.95 4.96 5.02 5.03

n-Bromide Trichloroethylene n-Bromide Trichloroethylene n-Bromide Trichloroethylene n-Bromide Trichloroethylene25mm 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.019.0mm 96.0 94.3 95.0 95.8 96.8 96.3 95.3 96.8 97.612.5mm 83.7 81.2 79.6 83.0 87.3 84.1 82.1 83.4 84.69.5mm 75.2 71.3 71.1 74.6 78.1 79.9 74.1 75.5 76.74.75mm 49.6 46.4 47.1 48.7 50.0 50.5 49.3 50.1 50.32.36mm 34.1 32.0 33.2 33.1 34.3 34.8 33.2 34.3 34.81.18mm 24.4 23.2 23.5 24.0 24.6 25.9 24.0 25.0 25.0600um 16.5 15.7 15.5 16.1 16.6 16.2 16.4 17.0 17.1300um 9.2 8.3 8.4 9.1 9.3 9.8 9.4 9.4 9.8150um 5.4 4.8 5.1 5.2 5.4 5.6 5.5 5.5 5.875um 3.6 3.3 3.6 3.5 3.6 3.6 3.6 3.5 3.7% AC 4.70 4.56 4.60 4.72 4.73 4.67 4.61 4.60 4.61

Split Test 1

Regional Research Laboratoryn-Propyly Bromide Vs Trichloroethylene

R047-06

Split Test 1 Split Test 2 Split Test 3Target AC/Gradation

Split Test 4Sample A (12.5mm SP)

Split Test 2 Split Test 3 Split Test 4Sample B (19mm SP)Target AC/Gradation

Supplier of Trichloroethylene for Asphalt testing in Ontario.

Provide waste disposal and recycling systems for Ontario Asphalt testing labs.

Focus on N Propyl Bromide replacements for Trichloroethylene for Asphalt Testing and vapor degreasing.

Stock Tech Kleen ®* NPB for Asphalt applications

Solvent minimization can be achieved by using on-site recycling of Tech Kleen ®* NPB

Kersol can provide all of the necessary recycling equipment, test kits and stabilizer boosters to safely and effectively recycle solvents on site.

For Information on Tech Kleen ®* NPB For Information on Tech Kleen ®* NPB Replacement Chemistry for Replacement Chemistry for TrichloroethyleneTrichloroethylene Contact:Contact:Glenn Webber

Email: glennwebber@kersolinc.com

Phone: 416-923-9120 Fax: 416-923-9120

Email General: kersol@rogers.com