Integrated Technology Management of Value Added By-products from Rice Bran and Rice Bran Oil Its Scope and Usage

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1 Integrated Technology Management of Value Added Byproducts from Rice Bran and Rice Bran Oil Its Scope and Usage Dr R B N PRASAD Chief Scientist & Head Centre for Lipid Research CSIRIndian Institute of Chemical Technology Hyderabad rbnprasad@iict.res.in

2 CENTRE FOR LIPID RESEARCH IICT Established a Dedicated Facility for Vegetable Oils, Biodiesel and Lubricant Research

3 VALUE ADDED PRODUCTS FROM RICE RICE Husk White Rice Rice Bran Rice Germ Ground Rice Fufural Silicon Crude Oil Defatted Rice Meal Polysaccharide Dietary Fiber Gum Wax Acid oil Deodorizer Distillate Lecithin Fatty Acid Sterol Squalene Triglycerides Tocopherol Tocotrienol Cooking oil Salad oil Phytin Fine RiceMeal Hydrogenated Oil Phytic Acid Inositol Inositol Triphosphate Calcium Phosphate DiBasic Glycolipid Modified lecithins Bleached Wax Soap Hydroxyapatite Fatty Acid Glycerine Oryzanol Ferulic Acid Caffeic Acid Alkyd Resin Ferulic Acid Triacontanol / Octacosanol Dimer Acid Polyglycerol Titerpene Alcohol Vanillin Long Chain Fatty Acid Fatty Acid Ester Polyglycerol Esters Phytosterol Ferulic Ester

4 ALL THE PROBLEMS OF PROCESSING STARTS WITH THE QUALITY OF RICE BRAN

5 EXPLOITATION OF BYPRODUCTS Overall capacity utilization of bran production, solvent extraction and oil refining remains low due to large capacities installed Only way to balance the economics of bran extraction and oil processing is to exploit the byproducts obtained during processing for value addition IICT motivated several Industries to go for Value addition to the byproducts of the processing industry Developed a Number of Products and Processes using the Byproducts of Rice Bran Oil Processing Industry Transferred Many Products to Industries

6 Integrated Technology Management of Value added Byproducts from Rice Bran and RBO The moment rice bran milled from rice grain, the lipase present in rice bran gets activated and hydrolyzes the oil present in it.. Need to extract the oil at the earliest possible to arrest the increase in FFA Bran contains large amounts of silica and silica has to be removed for edible applications Bran particles should not enter into oil which may create lot of problems to the quality of oil and byproducts Integrated technology management is highly essential for the production of value added products with high quality from rice bran or rice bran oil...

7 PHYTIC ACID Hexa phosphoric acid ester of myoinositol (5% of Rice Bran) Anti cancer activity, Inhibitory effect on tumors, prevents the formation of calcium oxalate crystals in the kidney, Dentifrice formulations (mouth wash), Descaling and washing of printing plates Source of Inositol another biological active product

8 SUPER CRITICAL CARBON DIOXIDE EXTRACTION Attractive Alternative for Extraction Process Traditional Solvent Green Process IICT initiated work at 12 litre capcity Pilot Plant 100% Extractability Good Quality Oil Low Phosphorus Content (<20 ppm) in the oil Expensive Compared to Traditional Solvent Extraction Deoiled cake my be a very attracdtive source for good quality protein

9 COMPOSITION OF CRUDE RICE BRAN OIL LIPID CLASS Wt % Triglyceride 8090 Diglyceride 210 Monoglyceride 12 Free Fatty Acid 440 Wax 36 Phospholipids 12 Glycolipid 12 Steryl Esters 23 Oryzanol 12 Unsaponifiables 34.5 Sterols (Major), Tocopherols, Tocotrienols, Triterpenols Hydrocarbons A Different Oil Compared to Seed Oils...

10 VALUE ADDITION TO BYPRODUCTS OF RICE BRAN OIL PROCESSING INDUSTRY Foodgrade Lecithin Glycolipids GUMS Modified Lecithins Oryzanol SOAPSTOCK ACID OIL Fatty Acid Methyl Esters Triacontanol Octacosanol CRUDE WAX Bleached Wax Activation of Spent Earth SPENT BLEACHING EARTH Fatty Acid Methyl Ester Tocopherols Tocotrienols DEODORIZER DISTILLATE Sterols

11 γoryzanol is a naturally occuring component in rice bran and rice germ, consisting of a mixture five major ferulic acid ester of sterols and triterpene alcohols BRAIN Postmenopausal syndrome, Anti stress, Autonomic nerve WHOLE BODY Antiallergenic, Antoxidant Antiinflammatory STOMACH Antiulcer, Centrally acting stomach movement SKIN Elevation of surface temperature Activation of sebaceous glands Whitening agent METABOLISM Hypolipidemic, Hypocholesterolemic Anticolon cancer

12 Crude rice bran oil contains 12% of Oryzanol Rice bran oil soapstock, a byproduct in RBO chemical refinery contains 34% of Oryzanol Soapstock contains gums, waxes, pigments etc. difficult to handle Methodologies adopted at CSIRIICT to isolate oryzanol in enriched form from such complex matrix: Solvent Fractionation/Soap Noodles

13 CSIRIICT developed Synthetic oryzanol (>95% Purity: a mixture of campesterol, stigmasterol and βsitosterol ferulates) Prepared from Phytosterols Isolated from Soya DOD (Lab Scale) Campesterol Stigmasterol βsitosterol Syrian hamsters: Lipid profile (TC, TAG, HDLC and LDLC) and Body weights assessed on weekly interval basis. Both Natural & Synthetic Oryzanol Exhibited Similar Hypocholesteremic activity APPLICATIONS FOOD (98% pure) Soft Capsules, tablets, fortification with vegetable oil and other food products. COSMETICS (5% in emulsified form) Soap, Facial Wash, Shampoo, Lotion, lip balm, lipsticks etc.

14 RICE BRAN WAX 36% In crude oil Byproduct obtained during dewaxing Oil: 2070% CRUDE WAX Free fatty acids: 020% Wax: 2565% Resinous matter: 512%

15 RICE BRAN WAX Crude rice bran wax Organic solvent Resinous Matter Upgraded Wax Oil Bleaching agent BLEACHED WAX Indian and Japanese Patents Applications: Paper coating, Polish (floor, furniture, shoe), Fruit & Vegetable coatings, Adhesives, Greases, Electric insulation, Water proofing, Lubricants, Carbon paper, Printing inks, Type writer ribbons, Textile & Leather sizing, Candles, Cosmetics, Chewing gums, Pharmaceuticals PHYSICAL AND CHEMICAL CHARACTERISTICS M.P. ( C) A.V. S.V. I.V. Bleached rice bran wax (IICTH) Rice bran wax (FDA specifications) (max) (max) Carnauba wax

16 HYDROGENATED WAX Crude Rice Bran Wax H 2 / Catalyst Hydrogenated wax Applications: Shoe and Floor Polishes, Candles, Additive in Tyre Manufacture, Pharmaceuticals, Cosmetics etc. Product Specifications: Melting Point, C; A.V: Depends on the A.V. of Crude Wax; Iodine Value, 1015

17 PROCESS FOR TRIACONTANOL / OCTACOSANOL (POLICOSANOL) FROM RICE BRAN WAX Crude Rice Bran Wax (Oil + Wax) O Defatting Oil Defatted Wax ( ) n O ( ) n C44 to C60 Soap Saponification O ( ) n ONa + ( ) n OH Policosanol ( ) n Soxhlet Extraction Soap OH (C30, 25 to 30%; C28, 1015%) Triacontanol is useful for stimulating growth in a wide variety of plants, including agricultural crops such as corn, soybean, wheat, rice and tomatoes Oral preparations containing 0.55% of a mixture of higher fatty alcohol formulations were reported to be useful for the treatment of hyper cholesterolemia and hyperlipoproteinemia Octacosanol can block the formation of cholesterol in the liver In addition to preventing the formation of cholesterol, octacosanol can also help to clear the blood of "bad" cholesterol that is already present

18 COMPOSITION OF POLYCOSANOL / OCTACOSANOL Sugar Cane Wax Rice Bran Wax 1Octacosanol Triacontanol Dotriacontanol

19 PHOSPHOLIPID: A NEGLECTED MOLECULE IN INDIA India producing about 9.5 lakh tones of rice bran oil About 20,000 tons potential for rice bran lecithin No industry is producing rice bran lecithin in the country Lecithin (not even soya lecithin) Not yet introduced as NUTRACEUTICAL in the country As on today Phospholipid is a neglected molecule in the country Extraordinary potential to exploit rice bran lecithin globally as it is superior to soybean lecithin

20 COMPOSITION OF RICE BRAN GUMS / LECITHIN Glycolipids & Minor Constituents (1 to 5%) Oil (35 to 50%) GUMS (LECITHIN) Phospholipids (50 to 65%) Free fatty acids (Vary depending on crude oil) Composition of lecithin varies depending on the source of crude oil and processing conditions of degumming

21 PHOSPHOLIPID CONTENT & COMPOSITION OF SOME SELECTED VEGETABLE OILS Source % in oil PC PE PI (%) (%) (%) Soybean Rice Bran Rapeseed Sunflower Groundnut Cottonseed Palm

22 APPLICATIONS OF LECITHIN FOOD BAKING NUTRACEUTICAL & PHARMACEUTICALS COSMETICS AQUACULTURE ANTIOXIDANT

23 GLOBAL SCENERIO LECITHIN USASGE Commercial lecithin is currently available in more than 40 formulations Margarine 2530% Baking/Chocolate & Ice cream 2530% Technical Products 1020% Cosmetics 35% Pharmaceuticals 1012% Major Usages as: Emulsifying, Dispersing, Wetting, Penetrating, Modifying, Crystal Formation, Antidusting & Antioxidizing agent

24 MAJOR PHOSPHOLIPIDS PRESENT IN LECITHIN O CH 2 OCR 1 O CH O CR 2 O + CH 2 OPOCH 2 CH 2 N(CH 3 ) 3 O Phosphatidylcholine O CH 2 OCR 1 O CH O CR 2 O + CH 2 OPOCH 2 CH 2 NH 3 O Phosphatidylethanolamine O CH 2 OCR 1 O CH O CR 2 CH 2 O O OH OH P O OH HO OH Phosphatidylinositol OH R 1 and R 2 = C 15 = C 17 Hydrocarbon chains

25 WHY RICE BRAN LECITHIN IS UNIQUE? Lecithin Soybean Lecithin Rice bran Lecithin Rice bran Lyso lecithin Fatty acid (wt %) 16:0 18:0 18:1 18:2 18: Rice bran lecithin More Oxidative Stability due to Less PUFA Rich in Nutraceuticals: Contains Oryzanol, Tocopherol, Tocotrienol, Steryl Esters etc.

26 CONSTRAINS FOR MAKING GOOD QUALITY RICE BRAN LECITHIN Considerable amounts of fines and metallic impurities are present in the crude rice bran oil Gums are contaminated with fines if degumming is done without proper filtration of oil Fines effect the purity and functional properties of lecithin Chemical Refining: Only gum conditioning and the gums are separated along with soap stock No Lecithn!! Physical Refining: If Phosphoric acid degumming is practiced, lecithin is contaminated with phosphoric acid; Gums cannot be used as a source of lecithin due to the presence of acidic/basic contaminants

27 HOW TO PRODUCE GOOD QUALITY LECITHIN? Pretreatment To remove fines and metallic impurities by adopting suitable methodologies in the solvent extraction plant To use proper filtration methods using efficient micronic filters to removed the fines and unwanted impurities from crude oil before degumming as the lecithin produced is used for food applications Degumming To adopt water degumming method to remove hydratable phospholipids Water degummed oil to subject to enzymatic degumming to remove remaining hydratable and nonhydratable gums Consumption of low amounts of enzyme

28 LECITHIN AND LYSO LECITHIN CRUDE OIL Water Degumming Wet Gums Removal of water Lecithin (contains 3550% oil) Wet Lyso Gums Degummed Oil Removal of water Phospholipase A1 Degummed Oil (with low P ) Lyso Lecithin (Contains 25 30% oil)

29 RICE BRAN LYSOLECITHIN Byproduct of Rice Bran Oil Enzymatic Degumming Process 100 TPD Plant produces around 1 to 1.5 Tons of Lysolecithin Contains Less Oil (1525%) Difficult to Convert into Soap Potential Applications Surfactant, Poultry feed

30 PHYSICOCHEMICAL PROPERTIES OF RICE BRAN AND SOYA LECITHIN Property Rice Bran Soya Acetone Insoluble (%) Hexane Insoluble (%) Moisture (%) Acid Value (mg KOH/g) Color (Gardner Scale) Peroxide Value (ppm) Oryzanol and other nutritional components (%)

31 RB Lysolecithin as a Source of Energy in Broiler Chicken Diet Collaborative Studies with Project Directorate on Poultry (ICAR) Proved as Good Energy Suppliment in Broiler Chicken Diet Trt. No Gum % in diet Body weight (g) 021 days 2235 days 21 days 35 days British Poultry Science, 52 (2011)

32 Slaughter Variables were Unchanged as energy supplement Serum Biochemical Profile was Comparable Tissue Protein and Fat Content were not Affected Growth of Different Organs were not Affected No Adverse Effect on Mortality Early Introduction of Lysolecithin had Additional Benefits on Performance of Chicks

33 VALUEADDED PRODUCTS FROM LECITHIN CRUDE LECITHIN Individual Phospholipid eg. PE, PC Bleached Lecithin Lecithin Enriched with Phospholipids Hydroxylated Lecithin

34 GLYCOLIPIDS FROM RICE BRAN AND SOYBEAN OIL GUMS Glycolipids Potent & Biologically Active Molecules Emerging area of research Vegetable Oil based Glycolipids Information are too sparse Polar lipid fraction enriched with glycolipids isolated using chromatographic techniques at laboratory scale IICT Developed a Process for the Isolation of Novel Phosphoglyceroglycolipid from Crude Rice Bran Oil Gums [US Patent Number 6,953,849 (2005)] O R 3 O O CH 2 H HO H C H O H HO H H C H O HO H O P O C H O O O R 1 R 2 OH H R 1, R 2, R 3, are fatty hydrocarbon chains IICT developed a formulation of gene carrying lipids in which glycolipids of rice bran showed its efficacy in delivering genes selectively to cancer cells.

35 DEODORIZER DISTILLATES A good source for fatty acids, tocopherols, tocotrienols and phytosterols [DOD contains triglycerides (3540%), free fatty acids (40 45%), tocopherols (18%) and sterols (2 10%)] Soybean deodorizer distillates exploited for value addition upto some extent Rice bran oil distillates has not yet exploited for value addition

36 R 1 HO R 2 O * CH 3 CH 3 CH 3 CH 3 CH 3 R 3 TOCOPHEROLS alpha Tocopherol (R1, R2, R3 = Methyl) beta Tocopherol (R1, R3 = Methyl, R2 = H) gamma Tocopherol (R1 = H; R2, R3 =Methyl) delta Tocopherol (R1, R2 = H; R3 = Methyl) R 1 HO R 2 O * CH 3 CH 3 CH 3 CH 3 CH 3 R 3 TOCOTRIENOLS alpha Tocotrienol (R1, R2, R3 = Methyl) beta Tocotrienol (R1, R3 = Methyl, R2 = H) gamma Tocotrienol (R1 = H; R2, R3 =Methyl) delta Tocotrienol (R1, R2 = H; R3 = Methyl)

37 COMPOSITION OF TOCOPHEROLS AND TOCOTRIENOLS (PPM) OF SELECTED VEGETABLE OILS Oil Tocopherols (ppm) Tocotrienols (ppm) Palm Soybean Sunflower Groundnut Corn Safflower Rice bran Wheat germ

38 STEROLS R HO Cholesterol R Sitosterol R Campesterol R Stigmasterol R

39 Sterol Content (mg / 100 g) and Composition (%) in Selected Oils Oil Sterols Brassicasterol Campesterol Stigmasterol Sitosterol Avenasterol Stigmasterol Avenasterol Canola / Trace Trace6 rapeseed Coconut Trace Corn 580 Trace 1023 Trace Trace 1,500 Olive Trace4 Trace Palm Trace Peanut Trace Trace Ricebran 350 Traces ,800 Sesame Soybean Trace Wheat germ 1,300 2,600 Trace 22 Trace

40 ERICHMENT OF TOCOPHEROLS, TOCOTRIENOLS AND PHYTOSTEROLS FROM RICE BRAN OIL DOD Tocol content in rice bran oil deodorizer distillate is very less compared to soybean/sunflower oil DOD Due to this reason, it is very difficult to enrich tocopherols, tocotrienols and phytosterols from rice bran DOD As Rice bran oil DOD is a potential source for tocotrienol it is worthwhile to cash this opportunity DOD conditions have to be fine tuned to enhance the tocol content IICT screened several DOD samples, but could not succeed in enriching Tocol concentration

41 STERYL ESTERS (Rice Bran Oil Contains ~23% Steryl Esters) R FATTY ACID PORTION O RCO STEROL PORTION Fatty acid Wt (%) Sterol Wt % 14:0 0.4 Campesterol : Stigmasterol :0 1.3 Sitosterol : Other sterols and : : :0 Tr 24:0 1.6 Triterpenols Cholesterol Lowering Property

42 SQUALENE COSMETICS Skin Protection creams PHARMACEUTICALS Reduction of Cholesterol & Triglyceride levels Cancer Therapy

43 CONCLUSIONS India has taken initiative for the Exploitation of Value added Products from Rice Bran and Rice Bran Oil Some Products have already been in the Market But Long Way to Go Rice Bran Oil R&D is full of Challenges and Opportunities Integrated Technology Management is Essential for the Production of High Quality Value Added Byproducts from Rice Bran and Rice Bran Oil

44 List of Patents of Centre for Lipid Research, CSIRIICT, Hyderabad, India On Refining of Rice Bran Oil and Value added Products from Processing Byproducts of Rice Bran Oil RICE BRAN OIL PHYSICAL REFINING SOAPSTOCK / ACID OIL RIC BRAN WAX SYNTHETIC ORYZANOL LECITHIN GLYCOLIPID Enzymatic Degumming of Rice Bran Oil using Phospholipase A1 Isolation of Gamma oryzanol from Rice Bran Oil Soapstock Upgradation & Bleaching of Crude Rice Bran Wax Ind. Pat: (2006) US Pat: (2009) Jap. Pat: Application pending China Pat: ZL Indonesia Pat: IDP Vietnam Pat: US Pat: 6,410,762 (2002) Jap. Pat: (2008) Ind. Pat: (2009) Ind. Pat: (2009) Jap. Pat: (2008) 1Triacontanol from Defatted Rice Bran Wax Ind. Pat: (2001) Preparation of Phytosteryl Ferulate (Equivalent to Natural Oryzanol) Acetylated Lecithin Hydroxylated Lecithin Isolation of Glycolipids from Rice Bran Oil Gums Specific Rice Bran Glycolipid and Phospholipids associated with Cationic Lipid Formulations Japan Pat: (2015) Ind. Pat: Application pending (2009) China Pat: Application pending (2011) US Pat: Application pending (2013) US Pat. No.: 6,403,344 (2002) Ind. Pat.: (2009) US Pat.: (2003) Ind. Pat.: (2006) Indian Patent (2009) US Patent Number 6,953,849 (2005) Indian Pat: Application pending (2012)s

45 THANK YOU Centre for Lipid Research, CSIRIICT