Laboratory Testing of Biodiesel

Ethanol DCO History

What is Biodiesel

Why test?

ASTM D 6751-10

Mark Fashian - President

BQ-9000 Critical 8

Process Control tests

One General Contractor

Mcgyan Bolt-On Process

Ethanol’s Distillers Corn Oil

(DCO) Extraction History

Early Adopters (only 5 or 6 for many years)

Why not extract high-value oil instead of leave in the DDGs as low-priced feed supplement?

Co-Product Diversification - pays off during market downswings, early adopters LTB

Rest of industry jumps on board (over 95% now)

Bolt-on Biodiesel Plants –we expect same cycle

Bolt-On Biodiesel in Ethanol –

Parallels DCO extraction history Early Adopters (only 5)

*According to Biodiesel Magazine 2018 Map

Why not convert DCO to high value biodiesel instead of sell to other biodiesel producers?

Co-Product Diversification - pays off during market down swings, early adopters LTB

Rest of industry jumps on board (Petro buy-in for RINs)

Biodiesel – FAME considered a D4 RIN=1.5/Gallon X Value

What is Biodiesel? Traditional Biodiesel Process

Triglycerides Alcohol +

Catalyst

(Lye)

Waste Products:

(Salt and Soap)

Glycerol + Biodiesel

100 lbs. 10 lbs. 10 lbs. 100 lbs. • Approximately the same mass of biodiesel results from the input triglyceride.

• New catalyst must be used for every batch & waste products water-washed out.

• Feedstocks: Distillers Corn Oil (DCO) & higher Free Fatty Acid (FFA) feedstocks

• Must acid acidulate high FFA feedstocks, like DCO or WVO, for process to work

• Approx. 10% of your 30 cent/lb. corn oil is downgraded to 10 cent/lb. glycerol.

O C ( = O ) R

O C ( = O ) R

O C ( = O ) R

R ' O H O H

O H

O H R ' O

O

R

R ' O

O

R H O

O

R R ' O H H 2 O

3 3 + +

+ +

TGs

FFAs

X

How to make high quality biodiesel

Quality testing a requirement

Send samples out to a contract lab

– $700-$1400 for a complete suite of ASTM D6751 tests

– Wait for days – wks

– Quality of data???

Test with your own internal laboratory

List of BAS reps across country

Biodiesel Laboratory Testing

Manual Testing –

labor intensive,

prone to mistakes,

holidays & sick days

Semi-Automated –

saves some labor

Possible errors

Fully Automated – push a button then walk away

removes 99% possibility of human error. Can hire

lower skilled technicians for lab.

BQ-9000 Critical Testing

Criterion for the Laboratory

BQ-9000 – what is it?

– Similar to ISO 9000 certification of processes or NELAC certification for laboratories

– Ensures quality on the manufacturing side

BQ-9000 Critical Testing Criterion

– Get new process in order – first seven batches require full suite of ASTM testing.

– Once the process is stable – only require the 8 most critical tests for each batch of biodiesel.

BQ-9000 Critical Test

ASTM D 6751-10 Specifications

NEXT 15 SLIDES DESCRIBE EACH SPEC.

Denotes BQ- requirement BQ-9000 Critical Test

10

FLASH POINT (D93)

MANUAL VS. AUTOMATED Spec: 130.0

degrees C minimum

Manual – dip flame every 2 degrees C until flash (1/2 hour)

Automated – load sample, type

in expected flash, push button &

walk away (2 minutes)

Labor: ½ hour Labor: 2 minutes

BQ-9000 Critical Test

WATER & SEDIMENT (D2709)

MANUAL ONLY Spec: 0.05 %

Max

Centrifuge sample to separate out sediments and water.

Heated oil centrifuge speeds up test.

Labor: 10 minutes

BQ-9000 Critical Test

KINEMATIC VISCOSITY (D445)

MANUAL VS. AUTOMATED

Automated – load sample, push button & walk

away with automatic cleaning cycle

Labor: ½ hour Spec: 1.9 to 6.0 mm2/S

Manual – time sample passing through glass tube – clean afterward

Labor: 2 minutes

SULFATED ASH (D874)

MANUAL ONLY

Spec: 0.02 %

Max

Burn and dry a

sample in a

crucible

Wash with acid

Forced air

muffle furnace.

Labor: 45 minutes

SULFUR (D5453)

MANUAL VS. AUTOMATED

Sensitivity to low ppb range

Manual – Risk of coking up system – injection rate of 1.2 ul/S is crucial

Automated – load sample, push button & walk away.

Required by distributors

Labor: 15 minutes Spec: 15 ppm

Max Labor: 2 minutes

BQ-9000 Critical Test

COPPER STRIP CORROSION

(D130) MANUAL ONLY Spec: No. 3 Max

Expose copper strips to fuel

to check for corrosion

Software available to

simplify test

Labor: 15 minutes

CETANE NUMBER (D613)

ENGINE VS. Cetane ID (Alt.) Spec: 47 min

Engine $250K

-$350K most

will send out

Ignition

Detector is

Half the price

& ASTM

approved for

alternate test

to Engine

Labor: 3/4 hour Labor: 2 minutes

CLOUD POINT (D2500)

MANUAL VS. AUTOMATED

Automated – ASTM D7399 - load

sample, push button & walk away

Labor: ¾ hour Spec: Report due in Dec.

Manual – Transfer tube from warmer to colder baths until wax crystals appear.

Labor: 2 minutes

BQ-9000 Critical Test

CARBON RESIDUE (D4530)

MANUAL VS. AUTOMATED Labor: 1/2 hour Spec: 0.05%

Max

Manual – Burn sample manually via ASTM D189

Automated – load sample, push button, walk away

Labor: 2 minutes

ACID NUMBER (D664)

MANUAL VS. AUTOMATED Labor: ¼ hour Spec: Max 0.5

mg KOH/g

Labor: 2 minutes

Manual – Prepare sample & manually titrate to endpoint

Automated – load sample, push button, walk away

Add glycerin purity, FFAs, salt in glycerin & Iodine Value

BQ-9000 Critical Test

FREE & TOTAL GLYCERIN (D6584)

MANUAL VS. AUTOMATED

Automated – weigh sample, place on workstation

push button & walk away

Spec: 0.24 % total Max (0.02 % Free)

Labor: 2 minutes Labor: 1 hour

Problem – Derivatization only lasts a couple hours

Manual – Add all internal standards & derivatization reagents by hand and inject by hand onto GC

BQ-9000 Critical Test

PHOSPHORUS, SODIUM, POTASSIUM

MAGNESIUM & CALCIUM (D4951)

MANUAL VS. AUTOMATED

Automated – load samples onto autosampler above,

push button & walk away - automatic cleaning cycle

Spec: 10 ppm P 5 ppm Na, K, Mg, & Ca

Labor: 2 minutes Labor: 3 minutes

Manual – ICP, load

sample w/ built-in pump

DISTILLATION (D1160)

MANUAL VS. AUTOMATED

VACUUM DIS. VS. SIM DIS Labor: 1.5 hours Spec: 360 C

Max at 90% recovered

Manual – Low precision & accuracy labor intensive, high service item

Labor: 2 minutes

Automated – load sample, push button, walk away. Uses same high-temp GC and workstation as ASTM D6584.

OXIDATION STABILITY

(D2274) AUTOMATIC ONLY Spec: 3 Hours Min.

Expose sample to high heat and oxygen to detect shelf life or rancidity

Software available to simplify test

Labor: 15 minutes

BQ-9000 Critical Test

Cold Soak Filtration

Newly added test to biodiesel Spec in 2008

BAS only laboratory provider supplying all

items needed for this test

ASTM Method number to publish soon

16 hour manual test

BQ-9000 Critical Test

PROCESS TESTS THAT MAY

BE REQUIRED BUT NOT ON

ASTM D 6751 Karl Fischer Moisture – ASTM D6304

Methanol Concentration – EN14110 (requires 2nd

oven w/ wax column – can replace Flash Point)

Biodiesel blends -EN14331- US $1/gal. tax credit

LIMS – Lab Info. Mgmt. System – for BQ-9000

Balance & Fume Hood & Lab Furniture

Lab Consumables – of course from MSI

TOTAL LABOR FROM ALL

ASTM TESTS ABOVE

MANUAL VS. AUTOMATED

Automated – Saves 6 hours per sample.

Plant size and sample volume different for every

biodiesel manufacturer.

BAS can customize a solution for you as your

biodiesel laboratory General Contractor (GC).

Labor: 7.7 hours Labor: 1.7 hours VS.

What is Biodiesel (continued) Mcgyan Biodiesel Process

Answers all the Traditional Process Issues • Approximately the same mass of biodiesel results from the input triglyceride.

• Mcgyan process yield is 99% w/w -

so higher than traditional process of 91-93%. • New catalyst must be used for every batch & waste products water-washed out.

• Mcgyan does NOT consume the catalyst - re-usable

zeolite catalyst. Also, Requires NO water wash. • Feedstocks: Distillers Corn Oil (DCO) & higher Free Fatty Acid (FFA) feedstocks

• Mcgyan can use any high FFA feedstock –

up to 100% FFA, thus saving $ on feedstocks. • Must acid acidulate high FFA feedstocks, like DCO or WVO, for process to work

• Mcgyan does NOT require concentrated acids/bases • Approx. 10% of your 30 cent/lb. corn oil is downgraded to 10 cent/lb. glycerol.

• Mcgyan Process does NOT make Gycerol hence your

improved yield($1/2M more per year profit)

Thank you for your attention.

Mark Fashian President, BAS

Global Sales Manager, Mcgyan Biodiesel

Local Rep, MSI in OH, WV, PA & NY

mark@biodieselanalytical.com or

Mfashian@midlandsci.com

Please call my cell at 740-815-2440 with any questions.