Ethanol Plant Testing-samples

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Testing includes:

GrainMashEthanol FeedWastewaterMethanatorEthanolMicrobiology ?

Typical Inbound Grain Tests Include:

Moisture (test weight lb/bu), crude protein, crude fat or oil, starch, damage and foreign material, dry matter, crude protein, crude fiber, calcium, phosphorus, sulfur, and ash.

Maize is composed of approx. 70 %starch, 8 % protein and 4 % fat/oil. The rest iscomposed of water, fibers, sugar andvarious mineral nutrients.

Wet Feed/Dry Feed/Syrup/Grain

Typical test I have done:

Moisture NIRCrude Protein NIRStarch NIRCrude Fiber NIRCrude Fat/Oil NIRAsh NIRCalciumPhosphorusSulfurAflatoxins? KITAntibiotic residue? Exp

Grain/Feed Data

Microsoft Office Excel 97-2003 Worksheet

Wet Distillers Grain (WDGS) Package

Moisture (overnight)Crude Protein (LECO)Crude FatAshCrude FiberAcid Detergent Fiber

(ADF)Neutral Detergent .Fiber (NDF)Net E nergies (NEL,

NEM, NEG )Total Digestible

Nutrients (TDN) Digestible Energy Metabolizable Energy Sulfur Calcium Phosphorus Potassium Magnesium Sodium Iron Manganese Copper Zinc

Environmental Labs need to be state certified:

Midwest LabsSDK LabsServi-tech*Magellan

Local??

Typical Tests for DDG Package

Color (L* Value)MoistureCrude ProteinCrude FatAshCrude FiberAcid Detergent Fiber

(ADF)Neutral Detergent .Fiber (ADF)Net E nergies (NEL, NEM,

NEG )

Nutrients (TDN)Digestible EnergyMetabolizable EnergySulfurCalciumPhosphorusPotassiumMagnesiumSodium IronManganeseCopperZinc

Syrup Typical Package

Moisture (Vacuum oven) Crude Protein (Kjeldahl) Acid Hydrolysis Fat Ash Crude Fiber Acid Detergent Fiber (ADF) Neutral Detergent . Fiber (NDF) Net E nergies (NEL, NEM,

NEG ) Total Digestible Nutrients (TDN) Digestible Energy

Metabolizable Energy Sulfur Calcium Phosphorus Potassium Magnesium Sodium Iron Manganese Copper Zinc

NIR or Send Out?

Whole Corn – Moisture, protein, oil, and starch.

Ground Corn – Moisture, protein, oil, and starch.

Mash – Total Solids. We will develop other HPLC test if you so desire

Cooker/Yeast Prop –Brix, DP4, DP3, glucose, maltose, glycerol, acetic acid, lactic acid, ethanol

Fermentation Samples – (same as above).

Beer Well -  (same as above). Wet Cake – Moisture, protein,

oil/fat, crude fiber, Acid Detergent Fiber (ADF), Neutral Detergent Fiber (NDF), starch, and ash.

Dried Distiller Grains – Moisture, protein, oil/fat, crude fiber, ADF, NDF, starch, and ash.

MASH TESTING ETHANOL TESTING

Solids Brix HPLC FAN pH HPLC NIR (as hplc) DE Yeast Counts Microbiology ?

Acidity Moisture Karl Fisher Apparent Proof pHe Chloride Levels Sulfate Levels Denaturant Heptane Methanol Specific gravity Gum IC Copper C of A’s ? ?

ASTM REQUIREMENTS FOR ETHANOL?

In House or Send Out?

Required ASTM (D4806) Testing on Ethanol and Denatured Ethanol

ASTM D5580 Aromatics ASTM D5580 Benzene   ASTM D6650 Olefins ASTM 5453 Sulfur ASTM 5191 Vapor Pressure ASTM D4052 Specific Gravity ASTM D4815 Higher Alcohols ASTM D130 Copper Corrosion ASTM D86 Distillation Curve to

include: initial boiling point 10% recovery, 50% recovery, 90% recovery and end point.

ASTM D5501 Ethanol & Methanol by GC    

ASTM D7319 Chloride & Sulfate by IC    

ASTM D6423 pHe     ASTM E1064 Water     ASTM D381 Gum

(washed/unwashed)     ASTM D1613 Acidity     ASTM D5453 Sulfur     ASTM E1688 Copper     ASTM D4052 Specific Gravity     Hydrometer Proof     VISUAL Appearance     Calculation Denaturant

Concentration

ASTM D4806 for ethanol used for fuel Property Limits Units

Ethanol 92.1 min. % v/v Methanol 0.5 max. (5,000 ppm) % v/v Water 1.0 max. (10,000 ppm) % v/v Solvent-washed gum 5 max. (50 ppm) mg/100 mL Chloride ion 40 max. (40 ppm) mg/L Copper content 0.1 max. (0.1 ppm) mg/kg Acidity as acetic acid 0.007 max. (70 ppm) %

w/w Appearance Visibly free of suspended or

precipitated contaminants Denaturant Minimum 1.96% v/v and maximum

4.76% v/v natural gasoline, gasoline components or unleaded gasoline.

Magellan E85 and Ethanol Testing

*Quarterly Denatured Ethanol Testing Requirements: Proof Apparent Proof ASTM E1064 Water by Coulometric Karl Fischer ASTM D5501 Ethanol Purity ASTM D6423 Determination of pHe ASTM D381 Existent Gum ASTM D512 Chloride ion ASTM D1613 Acidity of Ethanol ASTM D1688 Copper ASTM D5453 Sulfur **Monthly Denatured Ethanol Testing Requirements: Proof Apparent Proof ASTM E1064 Water by Coulometric Karl Fischer ASTM D5501 Ethanol Purity ASTM D6423 Determination of pHe ASTM D1613 Acidity of Ethanol Optional testing for an additional: ASTM D5827 Sulfate by Ion Chromatography ***Denaturant Testing Requirements: ASTM D5580 Benzene, Total Aromatics ASTM D6550 Olefins Optional testing for an additional:: ASTM D5453

ASTM Standards for Fuel EthanolPerformance Specifications

ASTM D 4806Standard Specificationfor Denatured FuelEthanol for Blending withGasolines for use asAutomotive Spark-Ignition Engine Fuel ASTM D 5798Standard Specificationfor Fuel Ethanol (Ed75-Ed85) for AutomotiveSpark-Ignition Engines

California Requirements Differ

ASTM D4806 (California)Parameter Limits Test Method FrequencyEach batch“calculated”Olefins, 0.5 D6550-00vol%, maxEach batch“calculated”Aromatics, 1.7 D5580-00vol%, maxEach batch“calculated”Benzene, 0.06 D5580-00vol%, maxQuarterlyThird partySulfur, ppm 10 D5453-93

California Denaturant Standards Parameter Limits Test Method

Frequency

Olefins, 10 D6550-00 Each batch vol%, maxAromatics, 35 D5580-00 Each batch vol%, maxBenzene, 1.1 D5580-00 Each batch vol%, max

Certificate of Analysis

Producer name and locationTraceable lot numberLoad dateQuality results, limits and test method usedQuarterly third party lab results statement

Shipping Samples:DOT Information:UN 1987, Alcohols, n.o.s.(ethanol, gasoline),Hazard Class 3, Packing Group IIShipping

DOT and PlacardsUN1987; Alcohols, (ethanol,gasoline)orNA1987; Denatured Alcohol

Fuel Ethanol E10 or E85?Place card: 1987

Degree of Polymerization by HPLC

DP

DP1=glucoseDP2=maltoseDP3=maltotriose DP4=maltotetraose DP5=maltopentaoseDP6=maltohexaoseDP7=maltoheptaose DP8=maltooctaose DP9=maltononaose DP10=maltodecaose

HPLC

DP = Degree of Polymerization

number of dextrose molecules linked together examples: DP1, DP2, DP3, DP4…DP10…

The extent of starch hydrolysis is expressed as Dextrose Equivalent (DE). DE is the percentage of glucosyl bonds that have been broken.

Dextrose is another word for D-glucose.

So, DE will be low (4 - 6) at the beginning of the process such as the Slurry tank outlet.

Meaning: Mostly large molecules exist and not many molecules of glucose.

DEXTROSE EQUIVALENT (DE)

When the DE is 100, all of the bonds between glucose units in the starch have been hydrolyzed. About 10% of the starch bonds are broken by the end of Conversion and up to half of the bonds are broken coming out of Saccharification.

If half of the starch bonds are hydrolyzed the average DP is 2 and the DE = 50

example: 25% DP1 + 25% DP3 + 50% DP2 = 50 DE

If a fourth of the starch bonds are broken the average DP is 4 and the DE = 25.DE determines the average DP length of the liquefied mash.

Estimation of DE from HPLC results

%DP1 * 100 + %DP2 * 50 + %DP3*33+ %DP4*10________________________________________

% Solids

= est. DE

MillingMixing

GelatinizationCooking

ConversionSaccharification

FermentationDistillation

Milling: Grind size effects– A large particle size can be more difficult to gelatinize

since enzyme cannot react with the substrate efficiently. This can result in yield loss (up to 10%).

– A small particle size (< 200 mesh) can also cause problems:

Mixing of floured grain in water may be more difficult.

Small particles will also cause problems in centrifugation, evaporation, and drying.

May have some positive effect on theoretical yield due to enzymes’ ability to react with starch.

Typical Size : Mill grain to 100% thru 16 mesh

Slurry: Gelatinization

The mash is cooked at 170 – 185 degrees to gelatinize most of the starch and break the viscosity enough to be pumpable.

Alpha-amylase and water molecules together are randomly breaking down (or hydrolyzing) the amylopectin (branches) part of the starch structure.

The alpha amylase produces a mixture of short sugar molecules (e.g. maltose, maltotriose), and some dextrin molecules (longer molecules of sugar).

4 - 6 DE mash

 

LiquefactionAlpha amylase is denatured in

Liquefaction primarily because of heat.

The heat further breaks down starch molecules for the second

addition of alpha amylase.

DE of 12 – 14

Purpose of Fermentation:

To produce ethanol through the anaerobic conversion of glucose by yeast.

51% of the glucose is converted to ethanol and 49% is converted to carbon

dioxide

Ethanol Level at end of Fermentation is typically 12 -

15% v/v.