Скачать презентацию Monitoring Biodiesel Fuel Quality National Biodiesel Conference User Скачать презентацию Monitoring Biodiesel Fuel Quality National Biodiesel Conference User

d803384f75b1e9aee8f09b6cdc22c821.ppt

  • Количество слайдов: 30

Monitoring Biodiesel Fuel Quality National Biodiesel Conference User Track – Fleet Implementation February 4, Monitoring Biodiesel Fuel Quality National Biodiesel Conference User Track – Fleet Implementation February 4, 2008 Randall von Wedel, Ph. D. Bio. Solar Group / Cyto. Culture Rv. [email protected] com

The (simplistic) Biodiesel Reaction + Liquid catalyst (potassium hydroxide) Combining Virgin crop oil, fat The (simplistic) Biodiesel Reaction + Liquid catalyst (potassium hydroxide) Combining Virgin crop oil, fat or recycled cooking oil (100 lbs. ) + Methanol (10 lbs. ) Yields Biodiesel (100 lbs. ) + Glycerine (10 lbs. )

Transesterification Reaction (basic) H O H - C - O - CH 2 CH Transesterification Reaction (basic) H O H - C - O - CH 2 CH 2 CH 2 CH 2 CH 3 O H - C - O - C - (CH 2)7 -CH = CH(CH 2)7 CH 3 + 3 H 3 - C -OH -------- + -OH O Methanol Catalyst H - C - O - C - (CH 2)7 -CH = CHCH 2 CH = CH(CH 2)4 CH 3 H Triglyceride Vegetable / Soybean Oil

Reaction releases biodiesel methyl esters from glycerin H H - C - OH H Reaction releases biodiesel methyl esters from glycerin H H - C - OH H O CH 3 - O - C - (CH 2)16 CH 3 Methyl Stearate (saturated ester) O + CH 3 - O - C - (CH 2)7 -CH = CH(CH 2)7 CH 3 Methyl Oleate (mono-unsaturated ester) O CH 3 - O - C - (CH 2)7 -CH = CHCH 2 CH = CH(CH 2)4 CH 3 Methyl Linoleate (di-unsaturated ester) Glycerin Biodiesel Methyl Esters Process Control and Batch Testing is Essential

Removing Residuals Ø Most transesterification reactions achieve 97 -99% conversion of oils & fats Removing Residuals Ø Most transesterification reactions achieve 97 -99% conversion of oils & fats to esters Ø Co-product glcyerin & unreacted reagents are largely removed by gravity separation or centrifugation; dissolved traces remain Ø Water washes remove last traces of catalyst, methanol, glycerin and soaps Ø Methanol is flashed off and recovered Ø Final polishing steps essential to remove traces of oils, mono- and di-glycerides and free glycerin to achieve ASTM spec

ASTM D 6751 Highlights Acid number – for aged, oxidized fuel Flashpoint – for ASTM D 6751 Highlights Acid number – for aged, oxidized fuel Flashpoint – for residual methanol Water & sediment – fuel fouling, deposits plus moisture in fuel accelerates oxidation Ø Sulfated ash – for residual catalyst Ø Bound glycerin – for incomplete conversion (mono, di and triglcyeride residues in fuel) Ø Free glycerin – inadequate fuel polishing Ø ASTM updates now include specs for Na+, K+, Ca++, Mg++ & oxidation stability Ø NEW “cold soak test” for sterols & glycerides Ø Ø Ø

Fuel Quality Control: A Mindset at 3 Levels from Plant to Fleet Ø Production Fuel Quality Control: A Mindset at 3 Levels from Plant to Fleet Ø Production at the plant: feed stock to fuel BQ 9000 or other rigorous QA program l ASTM 6751 specs and certification l Ø Distribution, storage and handling l l BQ 9000 or other rigorous QA program Protocols, documentation, monitoring Ø Consumer storage, dispensing & use l Protocols, documentation, monitoring

Biodiesel Fuel Specifications – Still a Quality Control Issue Ø Most or all problems Biodiesel Fuel Specifications – Still a Quality Control Issue Ø Most or all problems associated with biodiesel use are due to fuel quality issues, not to the biodiesel per se Ø Quality control problems largely a result of a rapidly growing industry, inexperience and lack of diligence. The problems are NOT caused by inadequate specifications or lack of proper methods and protocols, from the plant to the distributor to the user

Common Problems Associated with Bad Fuel Quality Most problems seen with B 100, not Common Problems Associated with Bad Fuel Quality Most problems seen with B 100, not B 20, but water & sediment are bad for all fuels Ø Most precipitates, sediments, bacteria, unreacted fats are macroscopic and caught by fuel filters Ø Residual catalyst & methanol degrade seals & gaskets that will harm fuel injection pumps Ø Residual glycerides, soaps, long chain saturated esters, unreacted fats leave deposits, foul engine, and degrade crankcase oil or cause polymers Ø Bacterial growth in contaminated tanks clogs filters and deteriorates the fuel Ø

Fuel Problems Associated with Increasingly Out of Spec Biodiesel Ø Residues in storage tanks, Fuel Problems Associated with Increasingly Out of Spec Biodiesel Ø Residues in storage tanks, filters and lines Ø Clogged filters can stop vehicles on road Ø Dissolved contaminants foul injectors Ø Coking of injectors and varnish on valves Ø Rough engine operation, smoke, wear Ø Catalyst, methanol ruin fuel injection pump Ø Crankcase oil deterioration, polymerization Ø Long term or catastrophic engine damage

Some problems get caught Ø Unreacted fats clog filters Ø Sediments, precipitates & bacteria Some problems get caught Ø Unreacted fats clog filters Ø Sediments, precipitates & bacteria get trapped But catalyst, methanol, acids, mono/di glycerides, sterols & free glycerin are dissolved in fuel

Mono & di glycerides result from incomplete transesterification H O H - C - Mono & di glycerides result from incomplete transesterification H O H - C - O - CH 2 CH=CH CH 2 CH 2 CH 2 CH 3 H-C-O-H H Monoglyceride (1 position; oleate)

Removal of Saturated Monoglycerides & Sterol Glucosides from Biodiesel Ø Avoid problem in first Removal of Saturated Monoglycerides & Sterol Glucosides from Biodiesel Ø Avoid problem in first place by removing sterol glucosides & phosphatides from oil during the degumming process Ø Polish biodiesel by passing over resins like aluminum silicates or diatomaceous earth Ø If precipitates with mono & di glycerides occur (e. g. , in transit), cold filter product Ø Worse case, chill product, let stand use gravity to settle ppts, then cold filter

Fuel Quality can Deteriorate Ø ASTM spec fuel that is improperly stored, transported and Fuel Quality can Deteriorate Ø ASTM spec fuel that is improperly stored, transported and handled can be ruined Ø Observed distribution problems include: l l l Storage tanks contaminated with water or old fuel (diesel or biodiesel); bacterial growth Trucks not clean; carry over residues to fuel Improper techniques for blending and fueling Aged fuel – oxidized, precipitates, sediments Mixed batches of fuel from various suppliers Oxidized (ruined) rail car loads last summer

Good Distribution Practices Ø Clean dry storage tanks, rigorous tank maintenance and routine testing Good Distribution Practices Ø Clean dry storage tanks, rigorous tank maintenance and routine testing programs Ø Inspection of each transport truck prior to loading; prior fuel only diesel or biodiesel Ø Certificate of Analysis for batch delivered Ø Proper blending, not just splash blending Ø Filtration of fuel to at least 5 microns Ø Protocols to prevent contamination Ø Paper trails from supplier to end user Ø Retain samples of B 100 for end user

Field Test Kit Developed for B 100: p. HLip Test A Quick Check in Field Test Kit Developed for B 100: p. HLip Test A Quick Check in the field for detecting traces of catalyst, mono/di/triglycerides, soaps, acids and oxidized (aged) fuel = hydroxyesters, peroxides Ø 10 min test; Simply add B 100 to test vial, mix by ‘flipping” & let the fuel float to create two phases Ø Visual indication only but quantitative capability Ø Unrelated to ASTM yet surprisingly sensitive for dissolved contaminants; Now a QC protocol test Ø Intended to alert a consumer or operator as a ‘firewall’, then they can request a formal lab test © Cyto. Culture 2006 Ø

Fuel Quality Test Concepts Extraction of catalyst or acid from fuel to aqueous p. Fuel Quality Test Concepts Extraction of catalyst or acid from fuel to aqueous p. H indicator elicits color change Soluble contaminants in biodiesel can be: >Extracted into the aqueous phase (fatty acid soaps) as visible turbidity >Concentrated at water-fuel interface (glycerides, sterols, oxidized esters) “Lens Effect” = Signal Amplification >Hydrated in the fuel as visible turbidity (mono, di & triglycerides; fatty acids) © Cyto. Culture 2006

Detection of catalyst contamination from poorly washed biodiesel fuels ‘Clear & Bright’ Reference Fuel Detection of catalyst contamination from poorly washed biodiesel fuels ‘Clear & Bright’ Reference Fuel Mirror Finish Neutral p. H Indicator Contaminated Biodiesel samples become turbid Alkaline p. H creates purple color; soaps cause turbidity © Cyto. Culture

Aging Oxidized B 100 Examples Relative to Fresh Bright Reference Fresh Bright Haze Smoke Aging Oxidized B 100 Examples Relative to Fresh Bright Reference Fresh Bright Haze Smoke Mirror Neutral p. H Acidic Residues © Cyto. Culture

Titration of Acidic Aged Biodiesel into Reference Soy Biodiesel Fresh Aged Acidic Indicator Solution Titration of Acidic Aged Biodiesel into Reference Soy Biodiesel Fresh Aged Acidic Indicator Solution Color Shifts from Red to Yellow with more Acid p. H = 7. 3 6. 4 4. 4 4. 0 3. 4 © Cyto. Culture

Test Color Shift is Linear with p. H in Acidic Range Test Color Shift is Linear with p. H in Acidic Range

Detecting near-spec and off-spec fuel : top vs. bottom of rail car Bright B Detecting near-spec and off-spec fuel : top vs. bottom of rail car Bright B 100 Reference Fuel Mirror Top Sample Glycerides Bottom Sample Glycerides 0. 76% Monoglycerides, 0. 38% Diglycerides, 0. 62% Triglycerides 0. 31% Total Glycerin with <0. 005% Free Glycerin in composite

Monitoring B 99 Fuel Quality for Fleet Deliveries by Truck/Rail Bus Fleet Managers Testing Monitoring B 99 Fuel Quality for Fleet Deliveries by Truck/Rail Bus Fleet Managers Testing B 99 on delivery

Typical Results for Commercial ASTM Biodiesel Samples in CA Often find B 100 is Typical Results for Commercial ASTM Biodiesel Samples in CA Often find B 100 is “Near Spec” (marginal ASTM fuel) Various feedstock B 100 samples from producers or retail stations The light “haze” is common for on-spec fuel; few have “Mirror Finish”

Rail Car Check with p. HLip Test Corroborates Lab Data (Soy biodiesel) Bottom Middle Rail Car Check with p. HLip Test Corroborates Lab Data (Soy biodiesel) Bottom Middle Top Bottom Sample Lab Result: PASS Total Glycerin = 0. 16%, Acid No. = 0. 12 mg KOH/g

“Biodiesel Quality Status Report” p. HLip Test Results and Lab Data TAN (mg KOH/g) “Biodiesel Quality Status Report” p. HLip Test Results and Lab Data TAN (mg KOH/g) ASTM D 664 MAX 0. 500 0. 12 KF Water (ppm) ASTM D 6304 N/A 205 Free Glycerin (mass %) ASTM D 6584 MAX 0. 020 0. 003 Monoglycerides (mass %) ASTM D 6584 N/A 0. 144 Diglycerides (mass %) ASTM D 6584 N/A 0. 010 Triglycerides (mass %) ASTM D 6584 N/A 0. 004 Total Glycerin (mass %) ASTM D 6584 MAX 0. 240 0. 160 Flash Point (deg C) 186 ASTM D 93 MIN 130 All Specifications Tested were PASS – typical rail car load

Out-of-spec, incompletely reacted B 100 Top Turbid fuel layer Free Glycerin (mass %) Monoglycerides Out-of-spec, incompletely reacted B 100 Top Turbid fuel layer Free Glycerin (mass %) Monoglycerides (mass %) Diglycerides (mass %) Triglycerides (mass %) Total Glycerin (mass %) Flash Point, Closed Cup (°C) Middle ASTM D 6584 ASTM D 6584 ASTM D 93 Bottom MAX 0. 020 N/A N/A MAX 0. 240 MIN 130 0. 000 0. 215 0. 523 1. 867 2. 605 50 Note ‘clear and bright’ B 100 samples vs. Turbid fuel layer in p. HLip Tests PASS N/A N/A FAIL

Oxidized (ruined) ASTM spec B 100 TAN (mg KOH/g) ASTM D 664 MAX 0. Oxidized (ruined) ASTM spec B 100 TAN (mg KOH/g) ASTM D 664 MAX 0. 500 0. 29 KF Water (ppm) ASTM D 6304 MAX 500? 736 Free Glycerin (mass %) ASTM D 6584 MAX 0. 020 0. 000 Monoglycerides (mass %) ASTM D 6584 N/A 0. 072 Diglycerides (mass %) ASTM D 6584 N/A 0. 007 Triglycerides (mass %) ASTM D 6584 N/A 0. 000 Total Glycerin (mass %) ASTM D 6584 MAX 0. 240 0. 085 Flash Point (deg C) 168 ASTM D 93 MIN 130 Oxidation Stability Index (Hr) EN 14112 MIN 3 2. 89 Cold Soak Filter Time (min) ASTM D 6217 b MAX 150 -250? 470 CSFA Particulate Ct (mg/L) ASTM D 6217 b < 50? 110

Biodiesel Quality Status Report Jan 31 TAN (mg. KOH/g) ASTM D 664 MAX 0. Biodiesel Quality Status Report Jan 31 TAN (mg. KOH/g) ASTM D 664 MAX 0. 500 0. 13 KF Water (ppm) ASTM D 6304 MAX 500? 725 Free Glycerin (mass %) ASTM D 6584 MAX 0. 020 0. 000 Monoglycerides (mass %) ASTM D 6584 N/A 0. 000 Diglycerides (mass %) ASTM D 6584 N/A 0. 019 Triglycerides (mass %) ASTM D 6584 N/A 0. 000 Total Glycerin (mass %) ASTM D 6584 MAX 0. 240 0. 019 Flash Point (deg C) 184 ASTM D 93 MIN 130 All Specifications Tested were PASS – Excellent (but moist) B 100

Conclusions on Monitoring Biodiesel Fuel Quality Ø “Stuff” happens (still!)…during production, distribution, and sitting Conclusions on Monitoring Biodiesel Fuel Quality Ø “Stuff” happens (still!)…during production, distribution, and sitting in end user’s tanks Ø Most common production issues: partially reacted fuel (high glycerides) + sterols Ø Most common distribution issue: oxidation Ø Most common end user’s issue: dirty tanks Ø Monitoring is easy, inexpensive and fast Ø Field tests work as ‘firewall’ then lab tests Ø Work with professional team to set up QA