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The Chemistry of Chocolate:
Fermentations to
Crystallization Kinetics in the creation of a Cherry Cordial
Nicholas L. Rozzi, Ph.D.
Director Global Commercialization
Godiva Chocolatier, Inc.
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Laurent Besin
Technical Service and Application Manager
Barry Callebaut
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Presentation Outline
Reactions Covered • Fermentation
• Maillard Reaction
• Crystallization Kinetics
• Enzymatic Hydrolysis
Process Steps • Cocoa Bean Growth, Harvest
and Drying • Roasting of the Cocoa Beans
and Producing Chocolate
• Tempering of Chocolate
• Preparation of the Cherry
Cordial Filling
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COCOA BEAN GROWTH, HARVEST AND DRYING
The Fermentation Step
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The cocoa tree
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The cocoa tree Theobroma cacao
Height of the tree 10 to 26 ft. Diameter of the trunk 8 to 10 in. Oblong leaves 8 to 12 in.
The cocoa tree bears buds, flowers and fruits at the same time.
The pods are harvested over a period of several months. In West Africa there are 2 crops, the main
crop extends from October to January and the mid crop from may to July.
Tree growing area 20° latitude north and South. Requires a hot and humid climate Low altitude (2300 ft. max.).
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The cocoa tree - 3 species • FORASTERO
• Originally from the Amazon.
• Production: more than 70% of world production.
• West Africa : Ghana, Ivory Coast, Brazil
• Good quality beans, less chocolate flavor than the Criollo and Trinitario
• CRIOLLO
• Originally from Central America and some areas of Asia.
• Production : 5 to 8 % of world production.
• Fine chocolate flavor often described as mild nutty, full chocolate.
• TRINITARIO (Hybrids between Criollo and Forastero).
• Origin : Trinidad and Grenada.
• Production : +/- 20 %.
• Some part of Venezuela and Colombia, Papua N.G., Madagascar.
• Fine chocolate flavor often described as mild nutty, full chocolate, fruitiness.
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Harvesting cocoa pods
Cocoa pods are grown on the trunk and main branches of the tree Theobroma cacao.
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The cocoa pod
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Different Shapes of Pods
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De-Podding De-podding consists of breaking the pods with a piece of wood or a «machette», remove beans and the adhering pulp. Beans with pulp are then ready for fermentation.
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Fermentation
• Fermentation and drying of cocoa is of vital importance. – Must start no later than 24 hours – after de-podding.
• Objectives : – Prevent germination of the bean. – Separate the grain from the pulp. – Initiate chemical and enzymatic reactions
inside the beans. – Develop flavor and color precursor. – Lower astringency and bitterness
• Fermentation last two to seven days
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Drying
• After fermentation the beans are placed in trays or on the ground to dry.
• Sun drying is usually adequate. Bananas leaves are used for covering during rainstorms or at night.
• Drying reduces the water content, from 60 % to
7 %.
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The fermentation process begins with the growth of micro-organisms. In particular, yeasts grow on the pulp surrounding the beans. Insects, such as the Drosophila melanogaster or vinegar-fly, are probably responsible for the transfer of micro-organisms to the heaps of beans. The yeasts convert the sugars in the pulp surrounding the beans to ethanol. Bacteria then start to oxidize the ethanol to acetic acid and then to carbon dioxide and water, producing more heat and raising the temperature. The pulp starts to break down and drain away during the second day. Lactic acid, which converts the alcohol to lactic acid in anaerobic conditions, is produced but, as the acetic acid more actively oxidizes the alcohol to acetic acid, conditions become more aerobic and halt the activity of lactic acid.
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The temperature is raised to 40oC to 45oC during the first 48 hours of fermentation. In the remaining days, bacterial activity continues under increasing aeration conditions as the pulp drains away and the temperature is maintained. The process of turning or mixing the beans increases aeration and, consequently, bacterial activity. The acetic acid and high temperatures kill the cocoa bean by the second day. The death of the bean causes cell walls to break down and previously segregated substances to mix. This allows complex chemical changes to take place in the bean such as enzyme activity, oxidation and the breakdown of proteins into amino acids. These chemical reactions cause the chocolate flavor and color to develop. The length of fermentation varies depending on the bean type, Forastero beans require about 5 days and Criollo beans 2-3 days. Following fermentation the beans are dried. The oxidation reactions begun through fermentation continue during drying.
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ROASTING OF THE COCOA BEANS AND PRODUCING CHOCOLATE The Maillard Reaction
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Chocolate process overview
Fermenting & Drying Beans
Conching
Cleaning & Winnowing
Roasting & Grinding Nibs
Preparing Paste: Roller Refining
Bulk Liquid Delivery Molding
Packaging & Shipping
Harvesting Cocoa Pods / Twice a year
Cocoa Mass
Cocoa butter
COCOA POWDER
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Cleaning and Winnowing
Cleaning: sieved, de-dusted, de-stoned, metal removed.
Winnowing: beans are winnowed to remove the shells.
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Roasting and Grinding
Cocoa liquor
Cocoa powder
Cocoa butter
• Roasting: – Critical to determine aroma and flavor.
Nibs are freed of bacteria Nibs are ground
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Preparing the paste: roller refining
Sugar Cocoa liquor
Cocoa butter
Milk Powder
Minor Ingredients
Mixer
Refiner
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MAIN POINTS 1. Manual liquid addition 2. Automatic liquid addition 3. Bulk 4. Tipping station 5. Manual addition 6. Mixer: to make the mixes 7. Five roll refiner: refining 8. Conches: Conching 9. Magnet 10. Hammer mill 11. Sieve 12. (horizontal) finishing tank 13. (vertical) stock tank
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7 10
4 5 2&3 1
6
13
12 11
8 9
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MAIN POINTS 1. Addition of liquid and
solid ingredients 2. overpressure outlet
(sugar grinding) 3. lid for manual additions 4. Steering equipment 5. Load cell 6. Lock 7. Dosing screw 8. Conveyor belt 9. Liquid additions 10. Water jacket
Rev 15/05/00
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Cocoa is produced in tropical regions
TRANSPORT
DRYING
FERMENTATION
YIELD
COCOA BEAN
KERNEL
NIB
SHELL
The main countries : • Africa (60 % world production ) - Ivory Coast - Ghana • South America (15 % world production ) - Brazil - Ecuador • Asia and Oceania (25 % world production ) - Indonesia - Malaysia
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Cleaning of the particles Destoner Magnet Debacterisation Breaker Winnowing grinding stages
(from small pieces till fluid)
Raw cocoa beans
Roasting
Stones Metal Heath
Magnet
Cocoa- liquor tank CM
Chocolate production
Particles
(*) Alkalified cocoa powder
Grinding
Cocoa press
Cake
Cocoa butter CB
Cocoa powder CP
(**) deodorised cocoa butter
(*) alkalify: process to change the color and the taste. (**) decolorize / deodorizing (***) positiv e release
(***)
Output of the shells Moisture
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DRYING PROCESS
COLD AIR
WARM AIR
HOT DRY AIR
STEAM
HOT CONCENTRATED FULL-CREAM MILK
SPRAY ROLLER
FULL-CREAMED MILK
SKIMMED MILK
FAT
CONCENTRATED
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HOMOGENOUS MIX WITH A GIVEN CONSISTENCY
REFINING
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BEFORE
Particles surrounded with fat = Paste
AFTER
A lot of little particles which are only partly surrounded with fat = Powder
After the refining extra friction surface is created for which no fat is av ailable.
FLUID FAT
DRY POW DER PARTICLE
REFINING
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1 kg solid mass 1 kg fat
Size of the particles Surface to be covered
• Big particles till 1 mm • Small surface
FLUID
• Medium-sized particles till 200 µm • Big surface
PASTE
• Small particles till 40 µm • Very big surface
POWDER
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A specific time is necessary to reduce the thickness. When the thickness is reduced to the half, the length of the film will be redoubled. Of course, the necessary time will be redoubled too. When the thickness is again reduced to the half, the length of the film will be redoubled again. So again, the necessary time will be redoubled too …
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ROTATIONAL SPEED (tr/min)
FINENESS
1
2
3
4
5
TEMPERATURE (°C)
25 SLOWLY COARSE
150
250
350 FINE 30
50
40
35
30
PRESSION
REFINED POW DER W ITH FINAL FINENESS
FLOW KG / HOUR
GAP PRESSION
MIX
FAST
50
ROLL NUMBER
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‘DRIER’ MIX GOOD CONSISTENCY ‘MORE LIQUID’ MIX
• Maximum flow • Bigger particles • Short refining time
• Good flow • Good rolling time
THE RIGHT CONSISTENCY OF A MIX DEPENDS ON THE RECIPE AND THE REQUIRED FINENESS
• Minimum flow • Small particles • Too long refining time
• Not enough resistance to push open the rolls • The mix is not taken easily by the rolls
CONSISTENCY OF THE TEXTURE OF THE MIX
• The mix is taken easily by the rolls •The rolls are pushed open rather easily
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REFINING
REFINING
WRONG
RIGHT
=
Too short/to coarse OK OK OK
=
Too long / too fine
OK OK OK
1st
mix 2nd
mix 3rd
mix 4th
mix
1st
mix 2nd
mix 3rd
mix 4th
mix
The final fineness of the whole conche will be wrong: Consequence : problems with rheology and taste.
Final fineness OK
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POWDER
The desired flavor Comes close to the desired liquidity (ready for sampling)
CONCHING
• The respective ingredients are mixed according to the recipe • And then refined to the desired particle size (i.e. fineness)
LIQUID
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TEXTURE
• Flavor • Moisture content • Fluid rheology (flow behaviour of the product)
Default master schedule
Time-temperature curve
Quantity and type of the refiner flake
Mechanical energy (expressed by the amperage of the motor)
Lecithin- and fat additives (quantity & time)
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PUMP OUT CONCHING FILLING
FINE POWDER
COCOA BUTTER (FAT) EMULSIFIER
COCOA BUTTER -FATS - AROMATICS... ARE ADDED
25 t 35 t
STORAGE OF LIQUID CHOCOLATE OR MOLDING
OPEN
CONCH 1 CONCH 2 CONCH 3 RECIPE X RECIPE Y RECIPE Z CAN BE IDENTICAL OR DIFFERENT
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• Lecithin • Cocoa butter • Fats
Buffer tanks
22 um
Fats, Milk fat....
Lecithin added automatically
Flavor added by hand
40 um
70 um
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4 Sieve 5 6/10 tons balancing tank 6 20/25 tons balancing tank
MAIN POINTS 1 Conches 2 Magnetic filter 3 Hammer mill
7 Vertical storage tank 8 Liquid loading
1
2
3
5
6
7
8
4
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0
10
20
30
40
5060
70
80
90
100
0 30 60 90 120
150
180
210
240
270
300
330
360
390
420
450
480
510
540
570
600
630
660
690
715
735
minutes
Tem
pera
ture
target value temperature
Conch filling starts eg: 4 mixtures at 1 mixture / hour
Cold water ensures that the product temperature never goes beyond the target value
Too little self-friction present in the product in order to heat up the conch. Hot water helps to heat up the product
The conch heats up significantly due to the self-friction of the product
The conch is completely liquid now. Pumping-over commences
Liquifying starts: lecithin/cocoa butter are added
The conch is empty. A new cycle may start
End of conch filling
Chocolate Water
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Lecithin is a emulsifier. In some cases, other emulsifiers could be used, e.g. PGPR (polyglycerol polyricinoleate), ammonium phosphatide, ...
• Friction (viscosity) arises between the solid particles in the chocolate mass
• Lecithin reduces the friction, thereby improving the liquidity • The mechanism at work here is
as follows: a lecithin molecule has two ends:
• 1polar: this bonds with the solid particles
• 1 non-polar: this bonds with fat by enveloping the solid particles (with the lecithin), a “lubricated” friction is obtained
MAIN TOPICS
Lecithin
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TEMPERING OF
CHOCOLATE
Crystallization Kinetics
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→ Dark chocolate:
Cocoa and sugar particles dispersed in a continuous phase of fat crystals and liquid fat
Chocolate microstructure
Sugar
Cocoa solids
Matrix of cocoa butter
50 µm
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Chocolate microstructure
Image: courtesy of FTE (Ghent University)
sugar fat
cocoa
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Chocolate microstructure
Triglyceride Melting point Triglyceride fraction (%) in cocoa butter
SOS 42°C 27%
POS 38°C 37%
POP 35°C 17%
SOO 23°C 13%
POO 16°C 3%
Temperature 20°C 25°C 30°C 35°C
Solid fat content 79 % 74 % 52 % 1 %
Melting of about 16% of triglycerides above 23°C
Liquid fraction ≈ 20% at 20°C
Glycerol
3 fatty acids
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→ Why tempering chocolate (cocoa butter)?
Chocolate microstructure ~ tempering
Homogeneous or heterogeneous semicrystalline matrix (~ microstructure)
crystallization
Nucleation Crystal growth Cluster formation Interconnected 3D crystal network
T, time, shear
Liquid cocoa butter
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→ Why tempering chocolate (cocoa butter)?
Chocolate microstructure ~ tempering
cocoa butter polymorphs
γ α
βIV βV
βVI 33.5 - 37°C 29.5 - 33.5°C 27 - 29.5°C
18 - 22.5°C 13 - 18°C ?
βIII 22.5 - 27°C
melting T range:
stable
α βV βVI
Temperature /°C
Heat
flow
(DSC
)
Windhab (2011)
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→ Why tempering chocolate (cocoa butter)? ⇒ producing stable crystals (βV, βVI)
⇒ controlled solidification and contraction of chocolate in cooling tunnel ⇒ fat bloom stability, good snap, good melting behaviour, good texture
Chocolate microstructure ~ tempering
Chocolate tempering Fry & sons (1847)
β ’
βV
20°C
29°C
31°C
50°C
t
Seed tempering
Addition of:
tempered chocolate (callets)
or
cocoa butter seeds (e.g., Mycryo® powder)
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PREPARATION OF THE CHERRY CORDIAL FILLING Enzymatic Hydrolysis
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Enzymatic Hydrolysis to Create a Cherry Cordial
• Creation of the classic cherry cordial involves the inversion of sugar to provide the liquid filling that we all know and love
• Product consists of: – Classic chocolate shell, tempered as discussed in the previous section – Filling formulated to
• Deposit with a high viscosity • Liquefy over two weeks time
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Enzymatic Hydrolysis Overview
• Hydrolysis is the break-up of sucrose through the addition of the water to Glucose and Fructose – Via the addition of acid (acid hydrolysis) – Via the addition of enzymes (enzymatic hydrolysis)
• Common Reaction used to make Invert Sugar Syrups
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+ H20 & Glucose Isomerase
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Invertase Activity is Effected by pH and Temperature
020406080
100
30 50 70Enz
yme
Act
ivit
y (%
)
Temperature (°C)
Enzyme Activity vs. Temperature
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0
20
40
60
80
100
3 4 5 6 7Enz
yme
Act
ivit
y (%
)
pH
Enzyme Activity vs. pH
• Product is formulated to optimize the activity of the Invertase from a pH standpoint
• Post production aging conditions (time and temperature) are set based on the Temperature Activity
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Cherry Cordial Recipe
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Ingredient Percentage Purpose
Fondant 90% Body of filling
Corn (Glucose ) Syrup 7.5% Viscosity control
Flavors and Acids 1.5% Flavor
Invertase 0.5% Enzymatic Hydrolysis
Preservative 0.5% Control Microbial Growth
Plus 1 Maraschino Cherry
• Ingredients are mixed and heated to 32-35°C • Filling is temperature is monitored to keep from melting
the fat crystals in the chocolate shell • Final product is cooled and stored for 2 weeks
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Effect of time on viscosity of fillings using Invertase
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0
5000
10000
15000
20000
Filli
ng V
isco
sity
(cp)
Time (Hours)
100 RPM50 RPM20 RPM10 RPM5 RPM
Over time, the Invertase breaks down the sucrose molecules, causing the viscosity of the filling to reduce,
behaving more like a liquid.
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Finished Product
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Thank You
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