Presentation is loading. Please wait.

Presentation is loading. Please wait.

Citrus-Based Biorefinery - Opportunities and Challenges - Patrick L. Mills Dept of Chemical & Natural Gas Engineering Texas A&M University-Kingsville Kingsville,

Similar presentations


Presentation on theme: "Citrus-Based Biorefinery - Opportunities and Challenges - Patrick L. Mills Dept of Chemical & Natural Gas Engineering Texas A&M University-Kingsville Kingsville,"— Presentation transcript:

1 Citrus-Based Biorefinery - Opportunities and Challenges - Patrick L. Mills Dept of Chemical & Natural Gas Engineering Texas A&M University-Kingsville Kingsville, TX CREL Annual Meeting – Washington University in St. Louis Energy: From Molecular Transformations to Systems October 25, 2006

2 The New Departmental Plan

3 Starting References 2. R. J. Braddock, Handbook of Citrus By-Products & Processing Technology, Wiley-Interscience: New York, ISBN , 247 pp, Dan A. Kimball, Citrus Processing: A Complete Guide, 2 nd Edition, Chapman & Hall Food Science Series, Aspen Publishers, Gaithersburg, MD ISBN , 450 pp, T. R. Graumlich, “Potential fermentation products from citrus processing wastes,” Food Technology, 94-97, Dec W. Q. Hull, C. W. Lindsay, & W. E. Baier, “Chemicals from oranges,” Ind. Engng. Chem., Vol. 45, No. 5, , May R. J. Braddock, “Importance of by-products to citrus juice processing,” Fruit Processing, 5, pp (2004). 1. B. Kamm, P. R. Gruber, & M. Kamm (editors), Biorefineries – Industrial Processes & Products: Status Quo & Future Directions, John Wiley: New York, ISBN , 964 pp, April 2006.

4 Morphology of Citrus Fruit zest Pericarp or rind Orange Citrus segment wall Mesocarp or pulp 40 to 65 wt % juice 35 to 60 wt % waste Lipids - oleic, linoleic, linolenic, palmitic, stearic acids; glycerol & physterol Sugars - glucose, fructose, sucrose, galactose, xylose, rabinose, ….) Acids- citric, malic, tartaric, benzoic, oxalic, succinic Insoluble carbohydrates – cellulose, pectin Flavonoids, peel oil, pigments, vitamins, minerals, … Nutrient Composition of Citrus By-Products

5 Total World Annual Citrus Production* 70 to 105 million tons/yr 2000–2003 (avg’d) *USDA/FAS, 2003 Horticultural & Tropical Products Div.,Wash.,DC - Sour orange - Shaddock - Citron - Lime USA 21% Brazil 24% Med 24% ROW 31% C. Reticulata C. Sinensis C. Limon C. Paradisi C. Quanantium C. Grandis C. Medica C. Aurantifolia

6 Example: Florida Citrus Production* *USDOE, Office of Energy Efficiency & Renewable Energy MM = 1 x 10 6 Added Value From Juice By-Products 90 lbs/box

7 Citrus Juice Process & Material Balance Fresh Citrus Fruit 3000 b/hr 123,000 kg/hr Juice extractors Wet Peel 54,600 kg/hr 82% H2O Dryer Feed 25,600 kg/hr 61% H2O Press Cake 19,000 kg/hr 65% H2O Hammermill Reaction Time Presses Dryer 14,500 kg/hr Press Liquid 35,600 kg/hr 9 o Brix Citrus Juice Waste Heat Evap 30,000 kg/hr Oil Mill / Plant Waste Molasses 6400 kg/hr 9 o Brix 33.4 % Pellets 11,000 kg/h 10% H2O d-Limonene 140 kg/hr Molasses 4400 kg/hr 72 o Brix 66.6 % (Soluble Fraction) (Insoluble Fraction)

8 Process Flow for Citrus By-Products Fresh Citrus Fruit Residue (Ground or Chopped) Citrus Seeds Dried Citrus Pulp with Liquor Press Liquor Pressed Fresh Pulp Citrus Molasses Citrus Seed Meal Citrus Oils Dried Citrus Pulp (w/o Molasses) Dried Citrus Meal Pressure with Added Ca(OH) 2 Sold as Molasses Dried Citrus Pulp (with Molasses) Pelleted & Added Back to Pulp PressureSieved Dehydration Dehydrated without pressing Ca(OH) 2 added Addition Bampidis & Robinson, Animal Feed Sci. Tech. 128 (2006)

9 Distribution of Citrus By-Products Basis: Oranges = 40.8 kg/box; Juice Yield ca. 55%

10 Distribution of Orange Juice By-Products Basis: 2005 – 2006 USA Production of 695,275 MT Source:

11 Pectin & Pectic Acid Pectic Acid (D-Polygalacturonic acid) Pectin Molecule

12 Recovery of Pectin from Citrus Peel Pectin (a polysaccharide) - white, spongy inner part of the peel Pectin (a polysaccharide) - white, spongy inner part of the peel Significant yield loss & waste generation with conventional hydrolysis Significant yield loss & waste generation with conventional hydrolysis BackgroundOpportunity Significant growth in use of low-methodoxyl pectin as a Significant growth in use of low-methodoxyl (LM) pectin as a - Thickening or gelling agent - In formulated food applications (yogurt, milk, desserts, etc...) Method for extraction & conversion of high-methodoxyl (HM) pectin Method for extraction & conversion of high-methodoxyl (HM) pectin from citrus peels with high efficeincy New enzyme or catalysts for rapid conversion of HM to LM pectin New enzyme or catalysts for rapid conversion of HM to LM pectin Efficient methods for purification and formulation Efficient methods for purification and formulationNeeds

13 Citrus Peel Waste as a Bio Feedstock Represents ca. 40 to 50 % of citrus fruit Represents ca. 40 to 50 % of citrus fruit Dried pellets used as cattle feed supplement Dried pellets used as cattle feed supplement Second to corn as a source of feed nutrients Second to corn as a source of feed nutrients CaO added - neutralize & de-esterify pectin CaO added - neutralize & de-esterify pectin Diffusion controlled process w/molasses Diffusion controlled process w/molasses COM can exceed cattle feed selling price COM can exceed cattle feed selling price Contains soluble & insoluble carbohydrates Contains soluble & insoluble carbohydrates (glucose, fructose, sucrose, pectin, cellulose, (glucose, fructose, sucrose, pectin, cellulose, hemicelluloses w/ galacturonic acid, glucose, hemicelluloses w/ galacturonic acid, glucose, arabinose, xylose, … as monomeric units) arabinose, xylose, … as monomeric units)

14 Composition of Citrus Juice Processing Wastes (Wet vs Dry Material) Dry Material Higher polysaccharide concentration Greater potential yield of sugars Higher energy consumption vs wet Higher pectin vs wet material Wet Material Lower sugar content vs dry material Lower yield of sugars Lower energy consumption Hydrolysis of polysaccharides req’d

15 Composition of Alcohol Insoluble Solids (Cell Wall Fraction of Orange Peel)* (Cell Wall Fraction of Orange Peel)* Not Useful for EtOH Production Grohmann & Bothast, ACS Symp Ser. 566 (1994) Raw Materials for EtOH Production Fructose & glucose present in nearly equimolar amounts Fructose & glucose present in nearly equimolar amounts No starch is present, unlike other Ag resids No starch is present, unlike other Ag resids Some organic acids, e.g., galacturonic acid Some organic acids, e.g., galacturonic acid

16 D-Galacturonic Acid Structure - Formed by the hydrolysis of pectin - Can be converted to d-glucose

17 Conversion of Orange Total Peel Solids to Monomeric Sugars - Comparison of Various Treatments- Conversion of total peel solids to monomeric sugars by enzymatic and combined acid and enzymatic treatments. Left bar (Unt) of each pair represents a mean of results obtained by enzymatic treatment alone, without acid treatment. The right bar (Tr) of each pair represents the mean of results obtained by sequential acid and enzymatic treatment. The symbols above each pair of bars represent the enzymes (or combination of enzymes) used in the enzymatic part of the treatment (C=cellulase; P=pectinase;  - glucosidase). The last pair of bars, labeled I"PCG, represents results of a treatment with a mixture of pectinase, cellulase and ~-glucosidase in excess. The individual sugars released are marked on the right side of the graph (Ara=arabinose; Fru=fructose; Gal=galactose; Glc=glucose; G.A=galacturonic acid; Xyl=xylose). Grohmann, K.; Cameron, R.G;. Buslig, B.S Bioresource Technology 54 (1995) CCGPPCPCG

18 Products from Various Solubilization Methods

19 Enzymatic Hydrolysis of Orange Peel Conversion of total peel solids to reducing sugars during enzymatic hydrolysis of untreated orange peel ( ) and peel pretreated with 0-06% sulfuric acid at pH=2.0 at 100, 120 and 140°C for 10 min, respectively. Treatments: a No acid pretreatment;---<>. pH=2-0, 100°C, 10 min; ---o.... pH=2.0, 120°C, 10 min; pH=2.0, 140°C, 10 min.. Grohmann, K.; Cameron, R.G;. Buslig, B.S Bioresource Technology 54 (1995) Enzymatic w/o acid pretreatment Enzymatic w/dilute acid pretreatment

20 Effect of Particle Size on Enzymatic Hydrolysis of Cellulose Comparison of shake-flask and attrition methods for enzymatic hydrolysis of Whatman CF-11 cellulose. (  ) Unmilled control, (  ) ball milled, (  ) 60 g of glass beads, (  ) 136 g of stainless-steel beads, all with a shaker speed of 200 opm. (  ) Attrition at 200 rpm. Cellulase complex PP 158: 1 IU/mL and 2% substrate. Neilson M. J., Kelsey, R. G., and Shafizadhe F (1982). Biotechnology and Bioengineering, Vol. XXIV, pp w/o milling conv. ball milling Glass beads SS beads Attrition mill

21 Novel Hydrolysis Schemes of Citrus Peel Peel celluose & hemi-cellulose contain value-added glucose, sucrose,.. Peel celluose & hemi-cellulose contain value-added glucose, sucrose,.. Existing hydrolysis methods are slow (on the order of days) Existing hydrolysis methods are slow (on the order of days) Lack of basic understanding of hydrolysis kinetic-transport effects Lack of basic understanding of hydrolysis kinetic-transport effects BackgroundOpportunity Develop methods and process with significantly higher Develop methods and process with significantly higher conversion rates and selectivities to monomeric sugars Novel enzymes, catalysts, and reactor systems Novel enzymes, catalysts, and reactor systems Basic data on the reaction mechanism & kinetic-transport effects Basic data on the reaction mechanism & kinetic-transport effects Mathematical models for kinetics, transport, & reactor systems Mathematical models for kinetics, transport, & reactor systemsNeeds

22 Production of Orange Juice By-Products Basis: 2005 – 2006 USA Production of 695,275 MT Source:

23 Catalytic Oxidation of Limonene trans-carveol  -terpinyl acetate R-Limonene +O2O2 PdCl 2 / CuCl 2 HOAc 15 hr, pH = 6 or R-Limonene +O2O2 PdCl 2 / CuCl 2 tert - BuOH tert – BuOOH (aq.) tert-butyl peroxide derivatives + w/o LiClwith LiCl

24 Oxdn of Limonene - Product Distribution a. Conventional Wacker b. Wacker with t-BuOH & t-BuOOH

25 Functionalized Derivatives of D-Limonene Limonene & other mono-terpenes are recovered from citrus peel oil Limonene & other mono-terpenes are recovered from citrus peel oil Derivatives (alcohols, aldehydes, ketones, allylic ethers, carboxylic Derivatives (alcohols, aldehydes, ketones, allylic ethers, carboxylic acid esters, epoxides…) are useful in pharma, perfumery, flavors BackgroundOpportunity Limited literature exists on application to natural products Limited literature exists on application to natural products Synthesis of new molecules, specialty polymers, & materials Synthesis of new molecules, specialty polymers, & materials New organometallic catalysts for mono-terpene functionalization New organometallic catalysts for mono-terpene functionalization Fundamental studies on kinetics, mechanisms, multifunctional reactors Fundamental studies on kinetics, mechanisms, multifunctional reactors Novel multiphase microreactor system designs & mini-plants Novel multiphase microreactor system designs & mini-plantsNeeds

26 Example of a Flavonoid - Diosmetin A human CYP1A enzyme activity-inhibiting natural flavonoid. A human CYP1A enzyme activity-inhibiting natural flavonoid. Diosmetin has antimutagenic and anti-allergic behavior. Diosmetin has antimutagenic and anti-allergic behavior.

27 Flavones & Flavonoids Naturally occurring aromatic secondary plant metabolites > 4000 have been identified in plants Positive health benefits - antioxidants- cardioprotective - antiviral- anticarcinogenic - antiallergenic Amount & type depends on citrus genus and agricultural growth factors

28 Novel Sepn & Conversion Methods for By-Products By-products (lignin, protein, limonene..) are produced in various By-products (lignin, protein, limonene..) are produced in various parts of the existing citrus process (hydrolysis, milling, etc.) Some behave as enzyme inhibitors, microbiocides, contaminants,… Some behave as enzyme inhibitors, microbiocides, contaminants,… BackgroundOpportunity Develop rxn-sepn methods or processes that convert these Develop rxn-sepn methods or processes that convert these to value-added products (flavors, perfumes, nutraceuticals,..) New enzymes, catalysts, and/or reaction-sepn processes New enzymes, catalysts, and/or reaction-sepn processes Insight and new data on mechanisms & kinetic-transport effects Insight and new data on mechanisms & kinetic-transport effects Mathematical models for the kinetic-transport processes Mathematical models for the kinetic-transport processesNeeds

29 Conclusions Citrus waste has potential as a biorefinery platform. Citrus waste has potential as a biorefinery platform. Notable differences vs corn & grain-based processes. Notable differences vs corn & grain-based processes. Conversion to EtOH represents one useful application. Conversion to EtOH represents one useful application. Specialty products would enhance economic potential. Specialty products would enhance economic potential. Various opportunities for novel enzymes, catalysts, Various opportunities for novel enzymes, catalysts, reactors, separations, & derivatives.


Download ppt "Citrus-Based Biorefinery - Opportunities and Challenges - Patrick L. Mills Dept of Chemical & Natural Gas Engineering Texas A&M University-Kingsville Kingsville,"

Similar presentations


Ads by Google