Surfactant and Quaternary Ammonia Toxicity in Anaerobic Fluidized Bed ReactorsMegan Kaiser

Bell’s Brewery

• Located in Kalamazoo and Comstock,

MI

• Package over 500,000 bbls of beer per

year (1 bbl is 31 gals)

• Generate ~220,000 gal of wastewater

per day

Bell’s Brewery at a glance

What’s the deal with Brewery wastewater?

•High sugar and alcohol = high BOD and COD• Average 12,000 ppm COD

•Beer has a pH of about 4.5

•Solids… hops, grain, and yeast• Average 3200 ppm TSS

Why Anaerobic Fluidized Bed Reactors @ Bell’s

Treatment Type

Examples KG CODper M3/d*

Industrial Installations (2016)**

Low Load Anaerobic Lagoon, Plug flow

1 262

Low Load ContinuousMixed Rxt

1-2 567

Medium Load

Anaerobic Contact Process

2-5 353

High Load Anaerobic Membrane,UASB

5-20 1,841 (1,622)

Very HighLoad

EGSB, FBR 20-40 1,213

Decreasin

g Foo

tprin

t and

HR

T

* - Modified from: van Lier, J. “After Anaerobic High-Rate Treatment: State-of-the-art New

Incentives.” Presented at the Anaerobic Experts Colloquium, Singapore. June 25, 2009

** - Modified from: Totzke, D. “Industrial Anaerobic Treatment Technologies and Design.” Presented at Marquette Anaerobic Treatment Short Course, Marquette University, September 13, 2016

Fluidized Bed Reactor Design

Reproduced from - Grady, Jr. C.P.L.; Daigger, G.T.; Lim, H.C. (Eds.) Biological Wastewater Treatment; Marcel Dekker: New York, 1999.

Why Anaerobic Fluidized Bed Reactors @ Bell’s

Treatment Type

Examples KG CODper M3/d*

Industrial Installations (2016)**

Low Load Anaerobic Lagoon, Plug flow

1 262

Low Load ContinuousMixed Rxt

1-2 567

Medium Load

Anaerobic Contact Process

2-5 353

High Load Anaerobic Membrane,UASB

5-20 1,841 (1,622)

Very HighLoad

EGSB, FBR 20-40 1,213

Decreasin

g Foo

tprin

t and

HR

T

* - Modified from: van Lier, J. “After Anaerobic High-Rate Treatment: State-of-the-art New

Incentives.” Presented at the Anaerobic Experts Colloquium, Singapore. June 25, 2009

** - Modified from: Totzke, D. “Industrial Anaerobic Treatment Technologies and Design.” Presented at Marquette Anaerobic Treatment Short Course, Marquette University, September 13, 2016

• Quaternary Ammonia Compound (QAC or quats)

• Great at killing bacteria

• Lysol

• Listerine

• Packaging line lubricants

• Surfactants

• Additive to our caustic soda used for CIPs

What’s the deal with QAC?

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

CO

Dre

m (

lbs/

d)

COD Removed CODrem (lbs)

Design CODrem (lbs)

Design 7-day Max rem

Timeline

• May ‘16 VA levels begin to climb (>400ppm) while sCOD removal falls (<85%)

• Mean Rate of Removal drops below 3000#COD/d (Sept ‘16)

• Screening Test to for caustic inhibition is positive. (Jan ‘17)

• Samples sent to VLB for analysis (Feb ‘17)

• Line Lube confirmed to contain trace levels of QACs (Feb ‘17)

• Line Lube replaced (Mar ’17)

• VLB Results Received (April ’17)

Chronology of Toxicity

Total Biogas FormationTotal Methane Formation

Testing and Figures By Dr. Alfons Arhens, VLB-Berlin

Respirometer Testing w/ Caustic Additives

0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

8,000

9,000

10,000

CO

Dre

m (

lbs/

d)

COD Removed CODrem (lbs)

Design CODrem (lbs)

Design 7-day Max rem

Timeline• Increased CIP frequency for

specialty brand packaging (April ‘17)

• Surfactants removed from built Caustic (June ‘17)

• Bell’s attempts and fails to reseed reactors on 3 occasions.

• Megan goes insane• Sara Martin presents “Critical

Decisions in Selecting Wastewater Treatment Technology” at MBAA annual conference (10/14/17)

Chronology of Toxicity (cont)

• Sample Collection Points• EQ Tank (Aqueous) • FBR 1 and FBR 3

• 50% aqueous phase• 50% Solids (media & associated biomass)

• Finished Effluent - aka post treatment (aqueous)

• Extractions• Weak – 5mM NaCl. • Strong - Dichloromethane.

• Sample Preparation• Standard – Prepared as described above• Solids – Samples centrifuged and

decanted prior to extraction• Spikes – 10 mg of each QAC or Surfactant

added to standard prep.

QACs Assayed

Non-Ionic Surfactants AssayedOctyl phenol ethoxylate polyoxyethylenesorbitan monooleate

Nonyl phenol ethoxylate lauryl alcohol ethoxylates

Polyoxyethylene stearate Palmitic acid ethoxylate

Polyoxyethylene propyleneglycol Stearic acid ethoxylate

polyoxyethylene mono-N-dodecyl-ether Myristic acid ethoxylate

Oleic acid ethoxylate

Tetradecyl pyridine benzyl ammonium chloride Diallyl dimethyl ammonium chloride

Hexadecyl pyridine benzyl ammonium chloride 3-methacrylamino-propyl thrimethylammonium chloride

Dioctyl dimethyl ammonium salt Diethylenetriamine-adipic acid polyamide

Decyl benzyldimethyl ammonium salt Octadecyl benzyl dimethyl ammonium salt

Dodecybenzylldimethyl ammonium salt Dodecyl dimethyl ammonium salt

Tetradecylbenzyl dimethyl ammonium salt Tetradecyl dimethyl ammonium salt

Hexadecyl benzyldimethyl ammonium salt Hexadecyl dimethyl ammonium salt

Cetyl Pyridinium chloride Benzyltriethylammonium chloride

Alkyl trimethyl ammonium bromides

Anionic Surfactants AssayedDodecyl sulfate sodium salt sodium dodecylbenzenesulfonate

Sodium stearate 4-sulfophenyl dodecanoic acid

Dodecyl sulfosuccinate Dioctylsulfosuccinate, Disodium salt

Experimental Design of Extraction for HPLC

0

20

40

60

80

100

120

Influent FBR 1 FBR 3 FBR 1 Solids FBR 3 Solids effluent

Tota

l QA

Cs

pp

m

Sample Collection Point

Weak Extraction of QACs (mg/L)

Decyl benzyldimethyl ammonium salt Dodecybenzylldimethyl ammonium salt

Tetradecylbenzyl dimethyl ammonium salt Hexadecyl benzyldimethyl ammonium salt

Octadecyl benzyl dimethyl ammonium salt Cetyl Pyridinium chloride

0

20

40

60

80

100

120

Influent FBR 1 FBR 3 FBR 1 Solids FBR 3 Solids effluent

Tota

l QA

Cs

pp

m

Sample Collection Point

Strong Extraction of QACs (mg/L)

Decyl benzyldimethyl ammonium salt Dodecybenzylldimethyl ammonium salt

Tetradecylbenzyl dimethyl ammonium salt Hexadecyl benzyldimethyl ammonium salt

Octadecyl benzyl dimethyl ammonium salt Cetyl Pyridinium chloride

Weak and Strong Extraction of QACs at Bell’s

0

20

40

60

80

100

120

Influent FBR 1 FBR 3 FBR 1 Solids FBR 3 Solids effluent

Tota

l No

n-I

on

ic S

urf

acta

nts

pp

m

Sample Collection Point

Weak Extraction of Non-Ionic Surfactants (mg/L)

Polyoxyethylene stearate Polyoxyethylene propyleneglycol

polyoxyethylene mono-N-dodecyl-ether polyoxyethylenesorbitan monooleate

lauryl alcohol ethoxylates Palmitic acid ethoxylate

Stearic acid ethoxylate Myristic acid ethoxylate

Oleic acid ethoxylate

0

20

40

60

80

100

120

Influent FBR 1 FBR 3 FBR 1 Solids FBR 3 Solids effluent

Tota

l No

n-I

on

ic S

urf

acta

nts

pp

m

Sample Collection Point

Strong Extraction of Non-Ionic Surfactants (mg/L)

Polyoxyethylene stearate Polyoxyethylene propyleneglycol

polyoxyethylene mono-N-dodecyl-ether polyoxyethylenesorbitan monooleate

lauryl alcohol ethoxylates Palmitic acid ethoxylate

Stearic acid ethoxylate Myristic acid ethoxylate

Oleic acid ethoxylate

Weak & Strong Extraction of Non-Ionic Surfactants at

Bell’s

Additional Test Locations

• FX Matt Brewing Company• Installed and operative January

2013

• 200,000 gallon reactor capacity

• Treating 6,000 #COD/d• Historic Max = 10,000 #COD/d

• Southern Tier Brewing Company• Installed and operative July 2016

• 30,000 gallon reactor capacity

• Treating 3,100 #COD/d• Historic Max = 3,100 #COD/d

• Treatment process includes solids settling and clarification before AD.

Weak & Strong Extraction at FX Matt Brewing

Company

0

20

40

60

80

100

120

Weak Strong Weak Strong

FBR 2 FBR3

QA

Cs

pp

m

Extration Type and Sample Location

Weak and Stong Extraction of QACs

Decyl benzyldimethyl ammonium salt Dodecybenzylldimethyl ammonium salt

Tetradecylbenzyl dimethyl ammonium salt Hexadecyl benzyldimethyl ammonium salt

Octadecyl benzyl dimethyl ammonium salt Dodecyl dimethyl ammonium salt

Tetradecyl dimethyl ammonium salt Hexadecyl dimethyl ammonium salt

Cetyl Pyridinium chloride

0

5

10

15

20

25

30

Weak Strong Weak Strong

FBR 2 FBR3

Tota

l No

n-I

on

ic S

urf

acta

nts

pp

m

Extraction Type and Sample Location

Weak and Strong Extraction of Non-Ionic Surfactants

Polyoxyethylene stearate Polyoxyethylene propyleneglycol

polyoxyethylenesorbitan monooleate

Weak & Strong Extraction at Southern Tier Brewing

Company

0

2

4

6

8

10

12

14

Weak Strong

QA

Cs

pp

m

Extraction Type

Weak and Stong Extraction of QACs

Decyl benzyldimethyl ammonium salt Dodecybenzylldimethyl ammonium salt

Tetradecylbenzyl dimethyl ammonium salt Hexadecyl benzyldimethyl ammonium salt

Octadecyl benzyl dimethyl ammonium salt Dodecyl dimethyl ammonium salt

Tetradecyl dimethyl ammonium salt Hexadecyl dimethyl ammonium salt

Cetyl Pyridinium chloride

0

0.5

1

1.5

2

2.5

3

3.5

Weak Strong

Tota

l No

n-I

on

ic S

urf

acta

nts

(p

pm

)

Extraction Type

Weak and Strong Extraction of Non-Ionic Surfactants

Polyoxyethylene stearate Polyoxyethylene propyleneglycol polyoxyethylenesorbitan monooleate

DAF Operations COD Reduction TSS Reduction

Bound QAC Reduction

(StrongExtraction)

Unbound QAC Reduction

(Weak Extraction)

With no chemicals 13% 61% 55% 32%With 200 ppm Flocculant 34% 93% 78% 51%With 200 ppm Flocculent and QuatNeutralizer dosedafter DAF 21% 86% 82% 61%With 200 ppm Flocculent and QuatNeutralizer dosed before DAF 34% 88% 96% 90%

With 200 ppm Flocculent and Coagulant 42% 92% 94% 90%

DAF Pilot Results

Conclusions:

• Built caustic “additive packages” can have acute and chronic toxic affects on FRB performance

• QACs & Surfactants adhere to some carrier particles, particularly hydrophobic surfaces.

• High solids loading contributes majority of biocidal compounds to reactors at Bell’s Brewery

Observations

• Reactors remain functional, but at reduced capacity with media carrying toxic concentrations of QACs & surfactants given constant operating conditions

• QAC & surfactant contamination of carrier particles appears to prevent biomass formation on media.

• Solids separation can reduce exposure of FBRs in brewery applications to QACs and surfactants.

Further Work:

• Continue to validate potential of solids separation to remove solids associated QACs and surfactants after equalization.

• Validate the potential to remove QACs and surfactants from media by:

• Direct Oxidation with strong catalyst(s)• Biodegradation under anoxic conditions• Biodegradation under aerobic condition

• Bench Testing began 6/10/18

Summary

• MWEA

• Dr. Clifford Lange, Auburn University

• Dr. Alfons Arhens, VLB Berlin

• Applied Technologies Inc.

• River Bend Labs

• Tyler Harvey & Rich Michaels, FX Matt Brewing Company

• Cyrus Padgett, Southern Tier Brewing Company

• Sara Martin, Critical Path Engineering Solutions

• VanAire Inc.

• Walker Modic

• Larry Bell

Thank You