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Citrus-Based Biorefinery - Opportunities and Challenges -. www.ars.usda.gov. www.praj.net. Patrick L. Mills Dept of Chemical & Natural Gas Engineering Texas A&M University-Kingsville Kingsville, TX 78363 Patrick.Mills@tamuk.edu. CREL Annual Meeting – Washington University in St. Louis

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slide1

Citrus-Based Biorefinery

- Opportunities and Challenges -

www.ars.usda.gov

www.praj.net

Patrick L. MillsDept of Chemical & Natural Gas Engineering Texas A&M University-Kingsville Kingsville, TX 78363Patrick.Mills@tamuk.edu

CREL Annual Meeting – Washington University in St. Louis

Energy: From Molecular Transformations to Systems

October 25, 2006

slide3

Starting References

1. B. Kamm, P. R. Gruber, & M. Kamm (editors), Biorefineries – Industrial

Processes & Products: Status Quo & Future Directions,

John Wiley: New York, ISBN 3527310274, 964 pp, April 2006.

2. R. J. Braddock, Handbook of Citrus By-Products & Processing Technology,

Wiley-Interscience: New York, ISBN 0471190241, 247 pp, 1999.

3. R. J. Braddock, “Importance of by-products to citrus juice processing,”

Fruit Processing, 5, pp 310-313 (2004).

4. Dan A. Kimball, Citrus Processing: A Complete Guide, 2nd Edition,

Chapman & Hall Food Science Series, Aspen Publishers, Gaithersburg, MD

ISBN 0834212587, 450 pp, 1999.

5. T. R. Graumlich, “Potential fermentation products from citrus processing

wastes,” Food Technology, 94-97, Dec 1983.

6. W. Q. Hull, C. W. Lindsay, & W. E. Baier, “Chemicals from oranges,”

Ind. Engng. Chem., Vol. 45, No. 5, 876-890, May 1953.

slide4

Orange Citrus

segment

wall

zest

Mesocarp or

pulp

Pericarp

or rind

Nutrient Composition of Citrus By-Products

www.infovisual.info

  • 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, …

Morphology of Citrus Fruit

  • 40 to 65 wt % juice
  • 35 to 60 wt % waste
slide5

Total World Annual Citrus Production*

70 to 105 million tons/yr 2000–2003 (avg’d)

C. Paradisi

USA

21%

ROW

31%

C. Limon

Brazil

24%

Med

24%

C. Reticulata

- Sour orange

- Shaddock

- Citron

- Lime

C. Quanantium

C. Grandis

C. Medica

C. Aurantifolia

C. Sinensis

*USDA/FAS, 2003 Horticultural & Tropical Products Div.,Wash.,DC

slide6

Example: Florida Citrus Production*

90 lbs/box

Added Value

From Juice

By-Products

MM = 1 x 106

*USDOE, Office of Energy Efficiency & Renewable Energy

slide7

Citrus Juice Process & Material Balance

Fresh Citrus Fruit

3000 b/hr 123,000 kg/hr

33.4 %

66.6 %

Juice extractors

Citrus Juice

Wet Peel

54,600 kg/hr 82% H2O

Oil Mill / Plant Waste

Hammermill

(Soluble Fraction)

Reaction Time

Press Liquid

35,600 kg/hr 9o Brix

Waste Heat Evap

30,000 kg/hr

d-Limonene

140 kg/hr

Presses

Press Cake

19,000 kg/hr 65% H2O

(Insoluble Fraction)

Dryer Feed

25,600 kg/hr 61% H2O

Molasses

6400 kg/hr 9o Brix

Molasses

4400 kg/hr 72o Brix

Pellets

11,000 kg/h 10% H2O

Dryer

14,500 kg/hr

slide8

Process Flow for Citrus By-Products

Fresh Citrus Fruit Residue

(Ground or Chopped)

Dehydrated without pressing

Ca(OH)2 added

Citrus Seeds

Pressure with

Added Ca(OH)2

Dried Citrus Pulp

with Liquor

Pressure

Press Liquor

Pressed Fresh

Pulp

Sieved

Dehydration

Dehydration

Citrus Oils

Citrus Molasses

Dried Citrus Pulp

(w/o Molasses)

Dried Citrus

Meal

Addition

Citrus Seed

Meal

Sold as

Molasses

Dried Citrus Pulp

(with Molasses)

Pelleted & Added

Back to Pulp

Bampidis & Robinson, Animal Feed Sci. Tech. 128 (2006)

slide9

Distribution of Citrus By-Products

Basis: Oranges = 40.8 kg/box; Juice Yield ca. 55%

slide10

Distribution of Orange Juice By-Products

Basis: 2005 – 2006 USA Production of 695,275 MT

Source: www.fas.usda.gov

pectin pectic acid
Pectin & Pectic Acid

Pectin Molecule

Pectic Acid (D-Polygalacturonic acid)

slide12

Opportunity

  • Significant growth in use of low-methodoxyl (LM) pectin as a
  • - Thickening or gelling agent
  • - In formulated food applications (yogurt, milk, desserts, etc...)

Needs

  • 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
  • Efficient methods for purification and formulation

Recovery of Pectin from Citrus Peel

Background

  • Pectin (a polysaccharide) - white, spongy inner part of the peel
  • Significant yield loss & waste generation with conventional hydrolysis
slide13

Citrus Peel Waste as a Bio Feedstock

  • Represents ca. 40 to 50 % of citrus fruit
  • Dried pellets used as cattle feed supplement
  • Second to corn as a source of feed nutrients
  • CaO added - neutralize & de-esterify pectin
  • Diffusion controlled process w/molasses
  • COM can exceed cattle feed selling price
  • Contains soluble & insoluble carbohydrates
  • (glucose, fructose, sucrose, pectin, cellulose,
  • hemicelluloses w/ galacturonic acid, glucose,
  • arabinose, xylose, … as monomeric units)
slide14

Composition of Citrus Juice

Processing Wastes (Wet vs Dry Material)

  • Wet Material
  • Lower sugar content vs dry material
  • Lower yield of sugars
  • Lower energy consumption
  • Hydrolysis of polysaccharides req’d
  • Dry Material
  • Higher polysaccharide concentration
  • Greater potential yield of sugars
  • Higher energy consumption vs wet
  • Higher pectin vs wet material
slide15

Composition of Alcohol Insoluble Solids

(Cell Wall Fraction of Orange Peel)*

Raw Materials for

EtOH Production

Not Useful for

EtOH Production

  • Fructose & glucose present in nearly equimolar amounts
  • No starch is present, unlike other Ag resids
  • Some organic acids, e.g., galacturonic acid

Grohmann & Bothast, ACS Symp Ser. 566 (1994)

d galacturonic acid structure
D-Galacturonic Acid Structure

- Formed by the hydrolysis of pectin- Can be converted to d-glucose

conversion of orange total peel solids to monomeric sugars comparison of various treatments
Conversion of Orange Total Peel Solidsto Monomeric Sugars- Comparison of Various Treatments-

C

CG

P

PC

PCG

PCG

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; b-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) 129-141

enzymatic hydrolysis of orange peel
Enzymatic Hydrolysis of Orange Peel

Enzymatic w/dilute

acid pretreatment

Enzymatic w/o acid pretreatment

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) 129-141

effect of particle size on enzymatic hydrolysis of cellulose
Effect of Particle Size onEnzymatic Hydrolysis of Cellulose

Attrition mill

SS beads

Glass beads

conv. ball milling

w/o milling

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 complexPP 158: 1 IU/mL and 2% substrate. Neilson M. J., Kelsey, R. G ., and Shafizadhe F (1982). Biotechnology and Bioengineering, Vol. XXIV, pp. 293-304

slide21

Opportunity

  • Develop methods and process with significantly higher
  • conversion rates and selectivities to monomeric sugars

Needs

  • Novel enzymes, catalysts, and reactor systems
  • Basic data on the reaction mechanism & kinetic-transport effects
  • Mathematical models for kinetics, transport, & reactor systems

Novel Hydrolysis Schemes of Citrus Peel

Background

  • Peel celluose & hemi-cellulose contain value-added glucose, sucrose,..
  • Existing hydrolysis methods are slow (on the order of days)
  • Lack of basic understanding of hydrolysis kinetic-transport effects
slide22

Production of Orange Juice By-Products

Basis: 2005 – 2006 USA Production of 695,275 MT

Source: www.fas.usda.gov

slide23

PdCl2/ CuCl2

+

O2

+

tert - BuOH

tert – BuOOH (aq.)

R-Limonene

tert-butyl peroxide derivatives

Catalytic Oxidation of Limonene

w/o LiCl

with LiCl

PdCl2/ CuCl2

+

O2

or

HOAc

15 hr, pH = 6

trans-carveol

a-terpinyl acetate

R-Limonene

slide24

b. Wacker with t-BuOH & t-BuOOH

Oxdn of Limonene - Product Distribution

a. Conventional Wacker

slide25

Opportunity

  • Limited literature exists on application to natural products
  • Synthesis of new molecules, specialty polymers, & materials

Needs

  • New organometallic catalysts for mono-terpene functionalization
  • Fundamental studies on kinetics, mechanisms, multifunctional reactors
  • Novel multiphase microreactor system designs & mini-plants

Functionalized Derivatives of D-Limonene

Background

  • Limonene & other mono-terpenes are recovered from citrus peel oil
  • Derivatives (alcohols, aldehydes, ketones, allylic ethers, carboxylic
  • acid esters, epoxides…) are useful in pharma, perfumery, flavors
slide26

Example of a Flavonoid - Diosmetin

  • A human CYP1A enzyme activity-inhibiting natural flavonoid.
  • Diosmetin has antimutagenic and anti-allergic behavior.
slide27

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
slide28

Opportunity

  • Develop rxn-sepn methods or processes that convert these
  • to value-added products (flavors, perfumes, nutraceuticals,..)

Needs

  • New enzymes, catalysts, and/or reaction-sepn processes
  • Insight and new data on mechanisms & kinetic-transport effects
  • Mathematical models for the kinetic-transport processes

Novel Sepn & Conversion Methods for By-Products

Background

  • 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,…
slide29

Conclusions

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