Challenges in Oils with High Chlorophyll Content Santiago de Chile August 2013 Jorge Bello Public Business Development 08.03.2013 Manager Canola – A Challenging Oil 08.03.2013 Phosphatides in crude oil % Unsaponifiable matter % Tocopherols % FFA % Waxes Chlorophyll ppm 0.05-0.10 0.19-0.44 0.04-0.07 2.5-5.0 absent <10 Canola oil 1.8-3.5 0.8-1.0 0.04300.2680 0.4-1.2 trace 10.0-60.0 Soybean oil 1.5-2.5 1.6 0.15-0.21 0.3-0.7 absent 0.5-8.0 Oil or Fat Palm Goals of a HA Adsorbent. High activity on chlorophyll Debottlenecking filter equipment. Improving throughput Reduction of: Oil losses; spent cake disposal and clay dosage. A beneficial Adsorbent Leaving most antioxidants in the oil. Reduction of Oil losses, spent cake disposal and clay dosage. Canola No 3 Western Canada Chlorophyll (ppm) Typical HA Adsorbent Dosage (%) Canola No 2 100 60 High Chlorophyll Short cycles 3.0 1.5 Canola No1 15 1.0 Relative Filter Cycle (1) 1/3 2/3 1 Relative oil lost in cake (based on +300% +50% ref dosage) 2 Chlorophyll is a Pro-Oxidant 08.03.2013 A great amount of antioxidants (carotenoids, tocopherols, etc.) have been removed from RB oil and the most from RBD oil. The oil is now more vulnerable to the effects of light on the attractive transparent bottles. 3 Chlorophyll and Free Radicals 08.03.2013 When the chlorophyll molecule absorbs light energy (E) in processed oils two reactions can occur : 1.- The E is dissipated as heat (a great part when the oils are exposed to direct radiation) 3.- The E adsorbed is released as free radical initiating oxidation reaction. •e- 4 Oxidation of the a Positions 08.03.2013 a –linoleic acid •e- Ataque de a la molécula Radical libre Radical libre Peróxido Formación de hidroperóxidos • • • • • • Odor Bad Taste Rancidity Polymerization Low stability Yellowing 5 Natural Decomposition and Fixing 08.03.2013 Disabling enzyme high chlorophyll in seeds BLEACHING Description Adsorb. % DEODORIZATION Stability Heavy Metals (ICP) Chlorophyll COLOR ppm Y "A" R Y 70 10.04 ----70 70 70 COLOR OR CANOLA OIL --- R 3.0 Adsorbente X Adsorbente Y SUP 1206 FF 1.0 1.0 1.0 1.9 2.0 3.0 BLEACHING:220°F, 30 min., 20 mmHg 0.25 0.34 0.12 1.1 0.9 0.8 9.0 10.0 7.1 OSI AOCM Cu P Ca Fe 120°C ---- 98.7°C ---- ppm < 0.05 ppm 7.98 ppm 9.77 ppm 0.13 4.10 4.50 5.00 19.35 21.29 23.71 < 0.05 < 0.05 < 0.05 4.10 3.73 < 0.4 5.13 4.03 0.57 Mg Total ppm ppm 2.81 20.69 < 0.06 1.49 10.72 < 0.06 1.21 8.97 < 0.06 0.28 0.85 DEODORIZATION: 480°F 120 min., 2 mmHg 6 The Role of Catalytic Acidity 08.03.2013 30000 25000 25000 Acidity reacts to attack the load centers 22000 22000 ppb 20000 15000 10000 Chlorophyll 5000 25 25 0 Crude Free acidity also attacks the bonds of the oxidant compounds. Acid Degumming neutralwashed RB RBD 6.5 7.0 6.0 PV 5.0 4.2 4.0 4.3 4.0 O II CH2- O-C –CH2-(CH2)n COOH Acid - Clay O II CH2- O-C –CH2-(CH2)n COOH O II CH2- O-C –CH2-(CH2)m –CH-CH2- COOH I O-OH O II CH2- O-C –CH2-(CH2)n COOH O II CH2- O-C –CH2-(CH2)n COOH O II CH2- O-C –CH2-(CH2)m 3.0 2.0 2.0 1.0 1.8 1.7 1.9 AV 0.0 0.0 0.0 Crudo Desgomado agua Desgomado acido RB RBD 7 Chlorophyll is Only Removed During the Bleaching Step 08.03.2013 COLOR CELL: 5 1/4" R A ANALYSIS CHLOROP HYLL “A” HEAVY METALS (ICP) ppm Cu ppm P ppm Ca ppm Fe ppm Mg ppm ppm CRUDE SOYBEAN OIL 10.0 70.0 0.59 nil <0.05 379.6 55.34 0.78 32.55 OIL FROM 1st. CENTRIFUGE 8.9 70.0 0.55 480 <0.05 11.73 0.08 0.18 0.42 OIL FORM 2nd. CENTRIFUGE 9.0 70.0 0.55 57 <0.05 3.26 <0.06 0.18 0.19 RB SOYABEAN OIL (Tonsil) RBD SOYABEAN OIL 8.7 1.0 70.0 9.0 0.02 ….. 0 0 <0.05 <0.05 <0.4 <0.4 <0.06 <0.06 <0.1 <0.06 <0.06 <0.1 Oil or Fat 700 600 590 550 550 Chlorophyll ppm Palm <0.100 400 Canola oil 10-60 300 Soybean oil 1-10 Corn oil <0.5 Palm Kernel Oil <0.2 Coconut oil <0.2 500 ppb SOAP 200 Chlorophyll 100 20 20 0 Crudo Desgomado Acido Neutro Lavado RB RBD 8 Chlorophyll Removed During Bleaching 08.03.2013 SAMPLES AND ANALYSIS OR CANOLA OIL (1") Ads BLEACHING COLOR: 5 1/4" CLOROFILA "A" R A ppm COLOR: 5 1/4" R A Cd 18-90 ANISIDINA DEODORIZATION Cd 12b-92 Ca 5a-40 STABILITY, Hrs. AGL OSI AOM % 120°C 97.8°C ------- P ppm Ca ppm Mg ppm 1.38 <0.06 0.63 ---- 4.5 72.3 21.24 --- --- --- TIPO SUP 1206 FF 1.2 7.3 70.0 0.170 1.8 9.0 5.95 <0.05 3.85 18.14 <0.40 <0.06 0.45 TIPO SUP 1206 FF 1.4 5.4 70.0 0.077 1.5 7.3 5.50 <0.05 4.10 19.35 < 0.40 <0.06 0.42 TIPO SUP 1206 FF 1.6 4.4 70.0 0.056 1.3 10.0 3.09 <0.05 4.30 20.32 < 0.40 <0.06 0.35 CONDITIONS : BLEACHING: 230°F,30 min.,20 mmHg. DEODORIZATION: 480°F,120 min.,3 mmHg. 7.00 Recommendations In RB oils Chlorophyll <100 ppb. Preference <50 ppb Adsorbent Dosage 1.2 6.00 1.4 1.6 5.00 4.00 3.00 Benefits Better Oxidative Stability. Oil with more stable color. 2.00 1.00 0.00 AnV Stability 9 Premium Products for Difficult Oils 08.03.2013 BLEACHING Adsorb. DESCRIPTION DEODORIZATION LOVIBOND % COLOR LOVIBOND Chlorop hyll A STABILITY, Hrs Heavy Metals Method (ICP) OSI AOCM Cu P Ca Fe Mg ppm ppm ppm ppm ppm < 0.05 1.39 0.62 0.13 0.42 COLOR R A ppm R A 120 °C 97.8 °C --- 7.9 70 2.06 --- --- ---- ---- ACTISIL FF 1.0 3.3 70 0.14 1.7 15 2.9 13.55 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1 SUPREME FF 1.0 2.2 70 0.01 1.0 7.4 3.6 15.00 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1 --- 10.0 70 0.81 --- --- ---- ACTISIL FF 0.8 6.3 70 0.11 1.2 8.7 4.6 21.77 < 0.05 13.5 SUPREME FF 0.8 4.0 70 0.02 0.9 7.5 5.4 25.64 < 0.05 10.6 < 0.06 < 0.06 < 0.1 --- 9.2 70 0.62 --- --- ---- ACTISIL FF 0.4 3.4 70 0.04 0.6 4.3 4.3 20.32 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1 SUPREME FF 0.4 3.8 70 0.01 0.5 4.4 4.6 21.77 < 0.05 < 0.4 < 0.06 < 0.06 < 0.1 OR SOYA OR SOYA OR SOYA BLEACHING:220°F, 30 min., 20 mmHg ---- ---- < 0.05 19.4 < 0.05 1.56 0.37 < 0.06 0.3 0.15 < 0.06 0.28 0.52 0.27 0.44 DEODORIZATION: 480°F,120 min., 2 mmHg For difficult oils Premium products show a better cost/benefit 10 Difference Between Activation Grades (Soybean Oil) 08.03.2013 100 1.8 Actisil Actisil 90 1.6 Supreme 80 1.4 70 Clorofila RB 1.2 Color RBD Supreme 1 0.8 0.6 60 50 40 30 0.4 20 0.2 10 0 0 Easy Oil Regular Oil Difficult Oil Easy Oil Regular Oil Difficult Oil The more difficult to bleach the oil, the greater the difference in cost/benefit between high activated grades and low activated grades 11 TOTAL Activation Patented Process 08.03.2013 O O O Si O Al O Si O O Al O Na+ O O Ca++Mg O O Si Si O O O Al O O O Al O O ++ K+ Fe+++ Al O O Si O O O O Al O Al O O O H+ O O Si Al O H2SO4 O H+ Na+ Ca++Mg++ K+ Fe+++ Na+ Ca++Mg++ K+ Fe+++ Na+ Ca++Mg++ K+ Fe+++ O O O Si O Al O Si O O Al O 90 O O Si Temperature O O Pressure Al O O m2/g O Time H+ Si O O Al O O O Al O Al O H+ O O O Si O O Si O O Al O Brönsted, Free Acidity Al O O 340 m2/g Acid Sites, Exchangeable Acidity, Lewis Acidity, Catalytic 12 State of the Art 08.03.2013 $ H2SO4,Temp, Time, Pressure, Work, Quality Before After Moisture 35 - 40% Moisture 10 - 20% pH Alkaline pH Acidic SA = 90 m2/g SA= 340 m2/g High Ion Exchange Low Ion exchange Heavy (45 lb/ft3) Light (34 lb/ft3) Slow Filtration Fast Filtration 13 TOTALLY Activated Surfaces 08.03.2013 Macro porosity in a particle of a TOTALLY Activated Adsorbent type 14 Laboratory Results 08.03.2013 25 20 15 10 5 0 22 15.6 Results: 18.8 17 BE dosage (%) 10R+Y (lovibond) 12 Chlorophyll (ppb) 10 5 1.2 Tonsil Supreme Improvement on the dosage rate approx. 25% Permeability 4.5 Slightly lower color after deodorization OSI (120°C) 1.6 20% higher throughput Commercial Adsorbent 10% higher stability. (more tocopherol left at the oil) Results: This could meant improvement in throughput specially for cases where bleacher is the bottle neck. Potentially this clay could be a good option for a packed bed system Chlorophyll (ppm) Reaction speed went fast 0.600 0.500 0.400 0.300 0.200 0.100 0.000 Commercial adsorbent Tonsil Supreme 5 10 15 20 25 30 Time (minutes) 15 Conclusions 08.03.2013 The goal of bleaching is to obtain a good quality finished oil. Bleaching effect should be measured after deodorization The most harmful impurities are invisible to the human eye, so measuring bleaching practices by color alone is not accurate Chlorophyll has a melting point of 248 ° F and is not distillable, but other oxidizing compounds decompose and are removed. Chlorophyll is only removed with adsorbents, and the higher the chlorophyll content, the greater the degree of activation that is required in the adsorbent. Carotene has a melting point of 356 ° F and is distillable however it is an antioxidant that ideally should be retained until distillation The color and RBD properties are important in assessing the role of the adsorbent Highly activated adsorbents are more efficient than adsorbents sprayed with acid 16 08.03.2013 Thanks / Gracias / Obrigado Anibal Urizar Technical Support LATAM Anibal.Urizar@clariant.com Jorge Bello Business Development Manager Jorge.bello@clariant.com