Enzymatic Oil Refining :

Transcription

1 Enzymatic il Refining : The Solution to Quality and Profitability W. De Greyt and M. Kellens Desmet Ballestra Group Zaventem, Belgium

2 Edible il Refining Purpose of refining of oils for edible uses is to remove undesirable substances and components while maintaining the nutritional quality and stability of the refined oil 1 Crude il REFINING Required refining capacity : > TPD Refined il Undesirable components - FFA - Phospholipids - Traces of metals - Pigments - Contaminants - Colouring components Quality requirements - Good stability - Good shelf life - Bland odor & taste - Good nutritional quality - Safe (no contaminants) - Healthy (vitamins)

3 Edible il Refining - Evolution Gradual improvement of the process technology * Processing under low vacuum (for oil quality reasons); * Evolution from batch to semi- to continuous operation (plant performance); * ptimized deodorization (low pressure, optimum heat recovery) * Milder processing, less chemicals (chem > phys) USE F ENZYMES 3

4 ENZYMATIC IL REFINING ILSEEDS Mechanical Pressing Solvent extraction il Extraction Deoiled Meal Enzymes in il Refining 1 4 Crude il Waterdegumming 3 Gums LECITHIN WDG il Soapstock Alkali Neutralisation 5 Acid Gums Acid degumming Bleaching Spent bleaching earth Bleaching Deodorization Deodorizer Distillate Physical deacidification Deodorization CHEMICAL Refined il PHYSICAL 4

5 Enzymatic il Refining: some proven, some under development and some waiting to be proven industrially Enzymatic Process bjective Status Miscella Degumming Max. PL removal + yield increase. n crude oil miscella (crushing plant) (Partial)Water Degumming Partial PL removal + yield increase. n crude, non-wdg oils (crushing plant) Gums Deoiling Full ( deep ) Degumming Bleaching Max. il recovery from wet gums n wet gums (crushing plant) Full PL removal + yield increase n waterdegummed oils (refining plant) Degradation of color pigments n waterdegummed oils (refining plant) Under development Industrially applied Ready for industrial application Industrially applied Under development Enzymatic il Degumming : industrially proven and well accepted Efficient degumming and higher oil yield 5

6 Enzymatic oil degumming The degumming process for the 1 st century finally come true? Phospholipase A1 Phospholipase A CH --C-R 1 Phospholipase B R -C--CH CH --P--X Phospholipase C Phospholipase D X = H, choline, ethanolamine, serine, inositol, etc. CURRENT SITUATIN Availability of more stable & (cost-) efficient enzymes Different enzymes/enzyme suppliers - Lecitase Ultra (PL-A1, Novozymes) - Rohalase PL-XTRA (PL-A, AB Enzymes) - Lysomax il (LAT, PL-A, Du Pont) - Purifine PLC (PL-C, DSM) - Purifine G/3G (PL-C + PL-A, DSM) Different approach - Increased oil yield as main driver - (Also) applied on crude oils 6

7 Industrial Enzymatic Degumming Source : * Worldwide : > 30 crushing/refining plants applying enzymatic degumming * Mostly soybean oil processors in Latin America and USA 7

8 Enzymatic water degumming Applied in crushing plants * n crude oil * With PL-C or PL-C/PL-A cocktails * Not for Lecithin producers Higher oil yield is main driver * Max. generation of diglycerides (from PL) * Some formation of FFA (also from PL) * Less oil entrainment in less gums Net revenue will depend on : * PL-content in crude oil (highest in soybean oil from expandates) * Price difference between WDG oil and meal (lecithin!) * Enzyme cost (enzyme price x dosing rate) 8

9 Enzymatic water degumming: PLC most preferred = = CH --C-R 1 R -C--CH CH --P--X = + H PLC CH--C-R 1 R -C--CH = = CHH + = H-P--X - - Phospholipids DIGLYCERIDES PHSPHATE-ESTER Yield increase : DAG + Less entrained Neutral il in less gums Commercial Enzyme Active enzymes Selectivity Conversion products Purifine - PLC PLC nly PC+ PE nly DAG Purifine - G PLC + PLA Mainly PC + PE Mainly DAG + some FFA Purifine - 3G PLC +PLA + PI-PLC PC + PE + PI Mainly DAG + some FFA 10

10 Enzymatic water degumming of soybean oil Crude soybean oil : Phospholipid composition Total PL (%) PC PE PI PA Crude oil Can be degraded by PLC Can be degraded by PI- PLC. theoretical DAG formation = PC*0, PE*0, PI*0,707 = 1.3% Enzymatic waterdegumming with Purifine 3G (=PLC +PLA +PI-PLC) Crude Enzymatic degummed FFA (%) Slight FFA increase (from PLA action) P Ca Mg DAG (%) No deep degumming (yet) 0.6% extra DAG (PLC action) = approx. 50 % of theoretical max. 11

11 Extra Revenue from Enzymatic Water degumming = 665 USD/ton SY Meal il = 50 USD/ton Jan 013 Sep 015 Average (01/013 09/015) : 400 USD/ton Average (01/010 09/015) : 550 USD/ton revenue : EDG-WDG (USD/ton) Revenue i.f.o. enzyme cost and (oil-meal) (oil-meal) (USD/ton) 1,5 USD/ton 3 USD/ton 6 USD/ton 1.8% oil yield increase Determining Factors Price difference oil meal Enzyme cost Achievable oil yield increase il and Enzyme dependent 1

12 Extra il Yield Increase from Enzymatic Water degumming % oil yield gain (max) 3,00,50,00 1,50 1,00 0,50 PTENTIEL YIELD GAIN PLC Enzymatic WDG with Purifine Canola/Sun soya TTAL N DAG VERENIUM DIGLYC D VERENIUM IL VERENIUM TTAL Enzymatic WDG of crude soybean oil with.5% phospholipds INDUSTRIAL DATA Enzyme il yield increase (%) Purifine - PLC Purifine - G Purifine - 3G , Source : Ventrici, E., Molinos.Data presented at the 014 ACS Conference (rlando,fl) ppm P in crude oil DAG : Diglycerides N : Neutral il Feedstock dependent (ppm P) Highest il Yield increase with Purifine 3G on crude soybean oil from expandates (max. P content) 13

13 Full deep enzymatic degumming Applied in crushing or refining plants * n crude or waterdegummed oil * With PL-A 1 or PL-A * Not yet fully proven with Purifine enzymes Degumming efficiency vs Yield increase * Efficient degumming (P < 10 ppm) required * Yield increase from formation of FFA and reduced entrained oil in gums * FFA will be stripped during refining and valorized as distillate Applications * Mainly on (crude) soybean oil, but also on other oils (rape, sun,...) * As part of the pretreatment process for biodiesel production * Missing link for physical refining of soft oils? 14

14 Full deep enzymatic degumming = = CH --C-R 1 R -C--CH CH --P--X = - + H PLA1 PLA CH H R -C--CH CH --P--X = = - = H--C-R Phospholipids Lyso-Phospholipids FFA + 1 Phospholipase- A1 (Lecitase Ultra, Novozymes) : most industrially applied Phospholipase-A (Rohalase PL-XTRA, AB Enzymes) splits off FFA at sn- position Conversion of ALL phospholipids in hydratable lyso-phospholipids and FFA Yield increase : FFA + Less entrained Neutral il in less gums Valorized as deodorizer distillate 16

15 Degumming efficiency vs Yield Increase Deep Enzymatic Degumming of Crude Soybean il Mmol/100g oil,5 1,75 1,5 1,5 1 0,75 0,5 0,5 10 min Lyso-PL PL Time (min.) P (ppm) FFA (%) ,34 0,44 0,68 0,84 0, Reaction time (min.) After 10 min. : good degumming (3 ppm P), but almost no yield increase ( FFA= 0.1%) After 10 min. : good degumming (7 ppm P), and good yield increase ( FFA = 0.5%) Reaction time required for yield increase 17

16 Applications Crude il DEEP ENZYMATIC DEGUMMING Lyso-Gums Extra biodiesel yield EDG il Silica treatment or washing Distillate FFA stripping Bleaching Acid Esterification Transesterification Distillate Physical deacidification Deodorization BIDIESEL Refined Food il meeting EN/ASTM specs Light color, bland taste Good stability No contaminants,... 18

17 Deep Enzymatic Degumming of Rapeseed il Enzyme assisted Acid degumming Acid assisted Enzymatic degumming il conditioning Citric acid (ppm) NaH (ppm) Enzyme reaction Enzyme dosing (ppm) Reaction time (hr) il quality FFA P Ca + Mg Crude il Rohalase PL-XTRA (PLA) Lecitase Ultra (PLA1) Deep enzymatic degumming (P < 5 ppm) is possible with PLA1 & PLA Correct acid conditioning and enzyme dosing is required 19

18 Deep Enzymatic Degumming for Biodiesel Production Crude Rapeseed oil Enzymatic degumming (50 ppm Lecitase Ultra 90 min.-55 C) Crude RS oil FFA :.40% P : 55 ppm Ca : 13 ppm Mg : 50 ppm Silica treatment (500 ppm citric acid 0.3% Silica) FFA stripping (35 C - 3mbar 1.5% steam 90 min) Refined RS oil FFA : 0.15% P : 0.9 ppm Ca/Mg : < 0.5 ppm BIDIESEL PRDUCTIN Good quality BIDIESEL MAG : 0.43% DAG : 0.1% TAG : 0.09% Free SG : 11 ppm Brilliant appearance 1

19 Enzymatic degumming : current situation Most widely applied enzymatic oil process Different enzyme (cocktails) are today commercially available Enzymatic waterdegumming or deep degumming Proven oil yield increase Conversion of PL in FFA or diglycerides Less neutral oil entrainment in the lyso-gums phase Why not applied more? Economical reasons (crude oil vs lecithin vs meal price) Process reasons (consistent full enzymatic degumming remains a challenge) Confusion (when to apply, on which oil, what to do with sidestream, dependency..) Is enzymatic gums deoiling an alternative?

20 Enzymatic gums deoiling : potential benefits Enzyme reaction Wet Gums Lyso-Lecithin + Recovered il 1. Applied on a side stream (wet gums) with no impact on the degumming process * Wet gums : 4-5% of crude oil flow (40-50 TPD vs 1000 TPD enzymatic degumming for SB). High flexibility * Can be applied depending on economics (lecithin vs oil vs meal) 3. Recovered oil (additional yield) is collected as separate stream * Can be recycled back to crude/wdg oil or valorized separately (e.g. biodiesel) 4. Potential Lower enzyme consumption (compared to oil degumming) 3

21 Recovered oil quality (from soy gums) FFA recovered oil (%) P recovered oil (ppm) FFA recovered oil (%) Correlation il recovery (% on N in gums ) P recovered oil (ppm) No Correlation il recovery (% on N in gums ) Soy gums with 41% moisture and 3% N on DM, ppm Lecitase Ultra, 4-6 hr at 55 C il recovery : up to 90% (on N in gums) = % on crude soy oil Recovered oil quality : FFA : 30-35% P-content : ppm 5

22 Conclusions Enzymatic oil processing appeals to the growing demand for milder and more sustainable refining; Today, enzymatic oil degumming is the only industrially proven enzymatic process in oil refining Enzymatic water degumming is successfully applied on crude soybean oil, but not yet with same success on other crude oils (too low P-content) Full enzymatic degumming is mostly applied in the pretreatment of soybean/rapeseed oil for biodiesel production. Enzymatic lecithin deoiling is an interesting alternative, ready to be tested industrially (PLC/PLA cocktail) 6

23 Thank you for your attention!! W. De Greyt and M. Kellens Desmet Ballestra Group Zaventem, Belgium Science Behind Technology 8