Good Golly Miss Moly!

Dan ParnellFlorida Industrial Pretreatment Association

Winter WorkshopFebruary 16, 2007

Overview

In the BeginningMoly RisingFinding MolyFree Moly!Moly Free is the Way to Be

Up in Smoke

Until 2002 – 5 regional Water Reclamations Facilities (WRF) sent sludge to central incineration facility.Incineration Issues:

• Air emissions• Ashes to the landfill• Power consumption

Biosolids FacilityCommissioned in late 2002

Produces 39 tons of biosolid pellets/day

Gravity Belt Gravity Belt ThickeningThickening

DigestersDigesters

CentrifugeCentrifuge

Polymer

Polymer

Methane

Methane

Nutrient Nutrient Enhancement

Enhancement

Problem

JEA Average Monthly Pellet Molybdenum Levels 1/04 - 7/04

0102030405060708090

Jan '04

Feb '04

Mar '04

Apr '04

May '04

Jun '04

Jul '04

Co

nc

. (m

g/k

g)

Limit 75 mg/kg

Moly Rising 40 CFR 503

40 CFR 503

Problem

Moly >75mg/Kg means:

Can not be land applied

Disposal Costs – averaging $2000/day for hauling/tipping fees

Loss of a $40 million dollar investment

IP Coordinator beginning to sweat

Finding Moly

ChallengesMoly internal or external? 85 Permitted Industrial Users> 850 square miles of service area

Finding Moly

Collecting Data5 Regional Water Reclamation Facilities

Inf/eff dataRaw sludge/pellets

Industrial effluent85 industrial users (IU) Where to begin?

Merck Index/web search

Finding Moly

Internal or External Source?Mass balance on Moly in raw sludge vs.

pellets. Results:Moly (in da raw sludge) = Moly (in da pellets)

External Source confirmed. Responsibility:

INDUSTRIAL PRETREATMENTINDUSTRIAL PRETREATMENT

IP Coordinator sweating a lot.

Finding Moly

Moly

(lb

/day)

Perc

ent

WRFCount

4.2 2.8 1.9Cum % 82.5 91.0 95.3 98.1 100.0

17.5 1.8 0.9 0.6 0.4Percent 82.5 8.5

SouthwestMandarinDistrict 2Arlington EastBuckman

20

15

10

5

0

100

80

60

40

20

0

JEA WRF Loadings (5/ 04 - 8/ 04)

C1

Indiv

idual V

alu

e

9/28/20049/21/20049/14/20049/13/20048/12/20047/29/20047/12/20045/27/2004

150

100

50

0

-50

_X=69

UCL=167.8

LCL=-29.8

C1

Movin

g R

ange

9/28/20049/21/20049/14/20049/13/20048/12/20047/29/20047/12/20045/27/2004

120

90

60

30

0

__MR=37.1

UCL=121.4

LCL=0

Buckman WRF Inf. Moly

82% of Moly from 1 Water Reclamation Facility – Buckman WRF

Influent Buckman WRF Moly data highly variable: Batch discharger?

WRF sampling resultsWRF sampling results

Finding MolyWhat is Moly?

Finding Moly

Research Results:Moly used in

Cooling tower chemical treatmentPetroleum lubricantsCatalyst for reactionsCorrosion inhibitor

Finding MolyCooling towers are

widespread in commercial, industrial, and institutional

applicationsIndustrial Uses of Moly: Cooling Towers (CT)

How do you quantify Moly loadings from CTs?

Data from CT chemical treatment vendors

estimated 12.5 lb/day of Moly

Ask the vendors that maintain them!

Finding Moly

Average Monthly Moly Levels in Pellets1/03 - 7/04

0

20

40

60

80

100

Co

nc.

(m

g/K

g)

winter

summer

winter

summer

Industrial Sources: Cooling Towers

JEAJEA

Finding MolyCooling Towers – are they the culprit? Lets do a little mass balance to find out!

Sample Date Inf Eff % removal

5/27/2004 144 53 0.637/29/2004 79.6 46.9 0.418/12/2004 91 48 0.479/13/2004 48 26 0.469/14/2004 42 28 0.339/21/2004 34 28 0.189/28/2004 76 34 0.55

0.43Average

Buckman WRF Moly Data

Average Moly removal rate at Buckman WRF: 43%

Estimated CT Moly loading: 12.5 lb/day.

12.5 lb/day * .43 = 5.4 lb/day in da pellets from CTs

It only takes 5.5 lb/day to reach the ceiling concentration limit!

Average WRF Inf. Loading: 21lb/day

12.5 = 21

Finding Moly

Centralized waste treaters, 2 of ‘em:

CWT A – 1.4 lb/day Moly

CWT B – 0.7 lb/day Moly

Industrial sources of Moly

Finding Moly

Industrial sources: CWT A

Observation

Indiv

idual V

alu

e3330272421181512963

5.0

2.5

0.0

_X=1.439

UCL=4.816

LCL=-1.938

Observation

Movin

g R

ange

3330272421181512963

4.8

3.6

2.4

1.2

0.0

__MR=1.270

UCL=4.148

LCL=0

11

11

CWT A Effluent Moly Loadings (lb/ day)

Moly spikes due to a single Moly used oil waste stream called “red oil”. Up to 5 lb in a day.

Finding Moly

Organic chemical manufacturer, 3 of ‘em, but only one used it as a catalyst:

• 4.5 lbs/day - consistent loading

Brewery - This Molys for you!Used in can rinse as a corrosion inhibitor: • 0.27 lb/day – consistent loading

Other Industrial sources of Moly

Finding MolyM

oly

lb/day

Perc

ent

Count7.3 3.7 1.4

Cum % 64.4 87.6 94.9 98.6 100.0

12.50 4.50 1.41 0.72 0.27Percent 64.4 23.2

20

15

10

5

0

100

80

60

40

20

0

Industrial Moly Sources

Total estimated industrial Moly loadings: 19 lb/day.

Actual daily average WRF Moly loading: 21 lb/day

19 lb/day ~ 21 lb/day

64% of Moly from CTs

Total estimated industrial loadings

More Fun w/ Mass Balances!

Free Moly! Local limit vs. Pollution Prevention

Long process

Affects everyone

Costly to re-engineer or pretreat for industries

Facilities w/ CTs to sample & report for compliance

Admin burden on IP to monitor CTs

There was an Moly free alternative

Substitution: >50% reduction in Moly

Minimal impact on customers

Minimal effort to implement

• Moly not an active ingredient in CTs• Moly used as a tracer

Free Moly!Pollution Prevention: Making the

Switch Find & Contact every facility w/ a

Cooling Tower=100’s

Contact 10 Known Chemical Treatment

Vendors

Agreed to switch to Moly free - eventually

Moly Free is the Way to Be!

Industry voluntary efforts: • IUs went CT Moly free

immediately• CWT dropped Moly laden “red oil”• Brewery switched to Moly free

can rinse

Fostering a collaborative relationship really paid off!!

Moly Free is the Way to Be!

Average Monthly Moly Levels in Pellets

0

20

40

60

80

100

Jul '04 Aug '04 Sep '04 Oct '04 Nov '04 Dec '04

Co

nc.

(m

g/K

g) Limit - 75mg/Kg

C1

Indiv

idual Valu

e

10/30/200610/2/20069/4/20068/7/20067/17/20066/19/20065/15/200610/27/20049/28/20048/12/2004

160

120

80

40

0

_X=33.8

UCL=72.4

LCL=-4.8

Before After

C1

Movin

g R

ange

10/30/200610/2/20069/4/20068/7/20067/17/20066/19/20065/15/200610/27/20049/28/20048/12/2004

100

75

50

25

0

__MR=14.5

UCL=47.4

LCL=0

Before After

1

1

Buckman Inf Moly Concentration Before/ After P2 Implementation

36% drop in Moly concentrations

Pellets return to re-use again – mid Sept.

Moly Free is the Way to Be!Current Status:• Best Management Practice for

Cooling Tower established.

• Local Limit eventually established.

• IP Coordinator still sweating.

Did not negatively impact customers

With Moly out of CTs – plenty to allocate

to the few industries that need it

But not as much and not over Moly!

Moly Free is the Way to Be!Conclusions

Returning biosolid pellets to marketable status was achieved through:Conducting data driven root cause analysis.Developing a simple yet effective P2 program.Implementing the program through collaboration w/ chemical vendors & industries.

Questions?