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Page 1September 2008 www.bucheralimentech.com
New Developments and Applications of Resin Systems for the Treatment of Citrus Products Containing Pulp and Cloud
ICBC September 2008
T. Schofield & C. Miller
Page 2September 2008 www.bucheralimentech.com
Citrus processing systems
1 cloudy products
2 clear products
Two Types of Resin Processes1 2
Page 3September 2008 www.bucheralimentech.com
Citrus Products Containing Pulp and Cloud
Juices - Orange and Grapefruit concentrates- Tangerine/Mandarin concentrates- NFC
Washes - WESOS (pulp wash)- Orange core wash
Extracts - Orange and Grapefruit peel- Tangerine/Mandarin peel- Lemon peel- Whole fruit comminutes
Page 4September 2008 www.bucheralimentech.com
Bucher Alimentech (BAN) Installations
36 CLOUDY CITRUS
MACHINES
36 CLEAR PRODUCTMACHINES
Page 5September 2008 www.bucheralimentech.com
Development of BAN Citrus Processing Technologies
1st Citrus processing equipment- 1984 Australia (debittering)
1st European installation- 1989 (Debittering and ratio adjustment)
1st USA installation- 1991 (Ratio adjustment/de-acidification)
1st Brazilian installation- 2007 (Debittering)
Page 6September 2008 www.bucheralimentech.com
Cloudy Citrus Products
Problems to be addressed• Bitterness - Limonin
- Polyphenols- Naringin (grapefruit)
• Astringency - Polyphenols (peel extracts)
• High Acidity
Page 7September 2008 www.bucheralimentech.com
Historical Solutions for Bitterness and Excess Acid
• Sugar was added to the juice to disguise bitterness
• In some countries alkalis were added to reduce the acidity of the products
Page 8September 2008 www.bucheralimentech.com
Limonin Bitterness Formation In Citrus Juices
C
OH
O
O
O
OO
O
(3) Limonoic Acid A-ring Lactone (non bitter)
OHO
H+O
O
O
O
OO
OO
A
A1 B
CD
(4) Limonin (intensely bitter)
C
O
O
O
O
OO
O
(1) Limonoate A-ring lactone-7-o-β-D-glucopyranoside (non bitter)
OO
OCH2OH
OHOH
OH
K
Limonin precursor synthesised in roots and stem and transported to the maturing fruit.
C
OH
O
O
O
OO
O
(2) Limonoate A-ring Lactone (non bitter)
OO
K+ Glucose
In the intact fruit (1) is converted to (2) in an Enzymatic controlled reaction. Enzyme confined to the neutral pH parts of the fruit flavedo, albedo, segment membranes, pith and seeds.
Enzymatic and acid induced conversion.
During the extraction, the Limonoate is dispersed into the acidic juice.
Page 9September 2008 www.bucheralimentech.com
Bitterness and Astringency*
* Astringency, a problem with peel extracts.
P495 only P495 & P685
Before After Before After
Absorbance of Total Polyphenolics (Petrus Method)
- - 3.60 0.41
3.30 2.12 3.30 1.58
Soluble Limonin (mg/L by HPLC) 70.0 1.50 70.0 6.60
Effectiveness of Resins
Resin system 1 Resin system 2
Note same resins effect on different starting materials in table – lines 1 and 2
Page 10September 2008 www.bucheralimentech.com
High Acidity
• Particularly at the beginning of a season with less mature fruit being processed
• In the USA high ratio (21~26) juice can be prepared using resins (21CFR 146.148)
• Will reduce the citric acid in the product, although the resins used will not materially affect the ascorbic acid (vitamin C) level
Page 11September 2008 www.bucheralimentech.com
Solution for Bitterness and High Acid
USE RESIN TECHNOLOGY
Types of Resin Technology
• Ion Exchange
• Adsorption
Page 12September 2008 www.bucheralimentech.com
Ion Exchange Applications
• Deionisation (DI)
• Acid Reduction (ratio adjustment)
Page 13September 2008 www.bucheralimentech.com
Ion Exchange
Deionisation- Applicable to clear juices- Recovery of natural sugars by removing minerals, salts, organic compounds including polyphenols, colour bodies and other products
CITRUS APPLICATIONS- Recover fruit sugars from citrus peels
Page 14September 2008 www.bucheralimentech.com
Ion Exchange
Acid Reduction- Applicable to all clear and cloudy products
CITRUS APPLICATIONS - Increase ratios of citrus peel extracts and
washes- Where allowed, is used for production of
low acid / high ratio orange juice
Page 15September 2008 www.bucheralimentech.com
Deacidification – Ascorbic Recovery
Ascorbic Acid
• Inlet: 440mg/kg
• Outlet: 421mg/kg(composite of cycle)
Graph 1: Citrus Deacidification - 10 000 litres/hour. Ascorbic acid Sam pled During the Run.(Initial ascorbic level = 440 ppm ; Initial citric acid concentration = 1.0 %)
Volume of Juice Processed (litres x1000)
0 2 4 6 8 10 12 14 16 18 20 22 24
Asco
rbic
Aci
d (p
pm)
0
100
200
300
400
500
600
Volume (x 1000 litres) vs Ascorbic Acid (ppm)
440421
Page 16September 2008 www.bucheralimentech.com
Adsorption Technology
• Debittering
• Reduction of Browning (Maillard)
• Hesperidin Reduction (clarified products)
Page 17September 2008 www.bucheralimentech.com
Adsorption
Debittering
Reduction of Limonin and Naringin
CITRUS APPLICATIONS- NFC
- Orange, Tangerine and Grapefruit Conc. - Orange, Tangerine and Grapefruit Peel- Orange and Grapefruit Washes- Whole Fruit Comminutes
Page 18September 2008 www.bucheralimentech.com
Adsorption
Colour Reduction
Reduction of Browning (Maillard reaction)
CITRUS APPLICATIONS- Clarified lemon juice - Peel extracts and comminutes
Page 19September 2008 www.bucheralimentech.com
Citrus Processing Resin Technologies
Bucher Alimentech (BAN) Cloudy Products System • Centrifuge resin columns with external resin
cleaning system
Others• Clarification by UF resin columns no resin
cleaning system (Bucher Alimentech use for clear products)
• Centrifuge resin without resin cleaning system
Page 20September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
UF Membrane + Debittering Columns
Page 21September 2008 www.bucheralimentech.com
Problems with UF System for Cloudy Products
• 100% cloud and pulp in one stream and 0% cloud and pulp in the other – recombination stability problems known
• Oil level must be below 0.01% (100 mg/l)• When there is membrane failure, pulp clogs the resin
bed, very difficult to clean – lost production• COST of Membrane replacement• COST of Energy • Temptation to run cycles too long – less resin cleaning
and risk of contamination – “The 4 a.m. Sunday syndrome”
Page 22September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
BAN Cloudy system diagram
Page 23September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
UF Membrane + Debittering Columns
Page 24September 2008 www.bucheralimentech.com
Advantages of BAN Cloudy System
• Processes cloud and pulp up to 1% - no enzyming required - good recombination
• Resin is completely cleaned and regenerated every 3.5 to 5 hours. No bacteriological contamination
• No oil problem – can process up to 0.1% (1,000 ppm)• If pulp gets into bed, immediately regenerate and
continue• Longer resin life• NO membrane costs• Energy costs significantly lower• TOTAL OPERATING COST MUCH LOWER
Page 25September 2008 www.bucheralimentech.com
Continuous debittering plant For cloudy juice 15,000 litres per hour (65 ~ 70gpm)
6.0m L x 2.3m W x 5.5m H(19’6” X 7’6” X 18’. approx)
Typical Processing Equipment
Page 26September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
Juice Process
Page 27September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
Resin Transfer and Wash
Page 28September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
Resin Return
Page 29September 2008 www.bucheralimentech.comSeptember 2008 www.bucheralimentech.com
Regenerate Resin
Page 30September 2008 www.bucheralimentech.com
Development 1 - NFC
• NFC is becoming more important • BAN process has been adapted to produce premium
quality• No separation of cloud from main stream important for
product quality• Dwell time in centrifuge + columns is much shorter
than in UF + columns – better product quality• Gas displace to minimize dilution
Page 31September 2008 www.bucheralimentech.com
NFC Gas Displace
Page 32
NFC Temperature Profile
September 2008 www.bucheralimentech.com
5
10
15
20
25
30
85
90
95
100
( 41 )
( 50 )
( 59 )
( 68 )
( 77 )
( 86 )
( 185 )
( 194 )
( 203 )
( 212 )
10 20 30 40
C( F )
TEMPERATURE PROFILE FOR BAN NFC ORANGE JUICE PROCESSING
(Actual Factory Conditions)TIME COMPARISON
EX FINISHER TO STORAGE
BAN NFC ……………..30 min
UF NFC ……………..55 min
BUFF
ER T
ANK
& PU
LP R
E-BL
ENDI
NG
EXTR
ACTI
ON
& FI
NISH
ER
CHIL
LER
BUFF
ER
TANK
DEBI
TTER
ING
ASEP
TIC
FI
LLER
S or
STOR
AGE
PULP
RE
DUCT
ION
BUFF
ER
TANK
Time min.
Page 33September 2008 www.bucheralimentech.com
Development 2 - Core Wash Debittering
• Traditionally UF has been used because of the type of pulp.
• The problem of separating core wash pulp by centrifuge has been solved.
• Core Wash is mainly cloudy (BAN system better)• Processing cost is high relative to product value.• The BAN system reduces the cost of processing by at
least 50%.• Energy consumption is reduced by at least 75%.
• BAN Debittered Product is judged better quality.
Page 34September 2008 www.bucheralimentech.com
Development 3 - Peel Extract Debittering
• Using BAN debittering the soluble solids can be upgraded to human food value
• The residual fiber can be used for human food also traditionally Animal Feed has been the end product
• This is an unstable market determined by factors outside the citrus industry
• The BAN system reduces the cost of processing and increases the output value
• Bio-actives can be produced from side streams
Page 35September 2008 www.bucheralimentech.com
Development 4 - Flexibility
New Possibilities
• If a company wishes to process different products during the season or out of season
• It is possible to change over the resin beds in the processing columns in less than 6 hours. This is not possible in other resin systems
Page 36September 2008 www.bucheralimentech.com
Resin Change - Over System
Page 37September 2008 www.bucheralimentech.com
Recommended Debittering Resin P495
Choice of Resin
• Bucher Alimentech is not tied to one supplier
• The best resin for an application is selected
• Resins meet USA and European regulations
Page 38September 2008 www.bucheralimentech.com
Service Life of Alimentech P495
Long service Life Alimentech P495
COMPARISION OF THE DEBITTERING ABILITY OF P495 AFTER 8 YEARS SERVICE WITH NEW ALIMENTECH P495.Feed Juice 35 ppm Limonin; Flow Rate 6 bv/hr.
Volume of Citrus Juice Processed (bed volume)
0 2 4 6 8 10 12 14 16 18 20 22
Abs
orba
nce
of T
otal
Pol
yphe
nolic
s (P
etru
s M
etho
d) &
Lim
onin
(mg/
L)
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Tota
l Fla
vono
ids
(mg/
L as
hes
perid
in)
0
500
1000
1500
2000
2500
3000
Solu
ble
Solid
s (o B
rix)
0
2
4
6
8
10
Abs325 of Polyohenolics - Used P495
Abs325 of Polyphenolics - New P495 Total Flavonoids - Used P495 Total Flavonoids - New P495Limonin - Used P495Limonin - New P495Soluble Solids (oBrix)
Page 39September 2008 www.bucheralimentech.com
Citrus Debittering - Typical Results
Feed OBrix Input (mg/L) Output (mg/L)
limonin naringin limonin naringin
Navel Orange Juice 12 13 - <1 -
Navel Peel extract 4 50 - <1 -
Valencia Peel extract 8 30 - <1 -
Kinnow 11 18 - <1 -
Grape fruit juice 10 25 600 <5 <250
Grape fruit peel extract
5 50 8000 <10 2000
Page 40September 2008 www.bucheralimentech.com
Costs
• Capital Costs (65 ~ 70gpm (15,000 l/h) plant) USD $ 800,000 (typical) Columns + centrifuge cost is no more than UF + columns cost
• Latest Brazilian costs show this system capital cost is less than the UF equivalent system
• Operating cost / ton (60~65OBrix product) • BAN Process: US$ 25~50/ ton• UF Membrane Process: US$ 100~130/ ton
Page 41September 2008 www.bucheralimentech.com
Benefits of BAN Process for Cloudy Products
• No alcohol or peroxide washes • No membrane replacement• Better recombination of cloudy products• Longer resin life• Low maintenance costs • Processes high oil products• Lower total operating cost
Page 42
Summary of Developments
September 2008 www.bucheralimentech.com
• NFC - Higher Quality- Lower Cost
• Core Wash - Better Quality- Lower Cost
• Peel Extract - Better Profitability- Lower Cost
• Flexibility – Short product change-over times
Page 43September 2008 www.bucheralimentech.com
Bucher Alimentech Systems
CITRUS MACHINES IN 13
COUNTRIES
TOTAL MACHINES IN 23
COUNTRIES
Page 44September 2008 www.bucheralimentech.com
Thank you!
Bucher Alimentech Ltd13 b Gabador Place Auckland 1060New ZealandP: +64 9 573 1333 F: +64 9 573 [email protected]