Advanced Hop Products:

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Advanced Hop Products Not Just for the Majors
MBAA Michigan District Presentation Mike
Babb January 15, 2009
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Hops

• Contribute to distinguishing one beer from
  another.
• Give beer most of its bitterness.
• Contribute distinctive flowery, herbal, spicy
  flavor and aroma to beer.
• Contribute to foam stability especially lacing
  in glass.
• Can assist in the hot and cold break,
  contributing to beer clarity.
• At elevated bitterness levels, have
  bacteriostatic properties.
• Can be a cause of flavor and colloidal
  instability
• Can be a source of off-flavors i.e., light-struck

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Hops2007 2008 Situation

• 2005 hop crop spot prices 30 - 40/kg a.
• 2006 hop crop spot prices 50 - 60/kg a.
• 2007 hop crop was sold out early. Spot prices
  were reported as high as 600 - 1,000/kg a.
• 2008 hop crop harvest for 2009 is 95 sold out,
  spot prices 150/kg a.
• 2009 hop crop harvest for 2010 is 75 sold out,
  estimated spot pricing 120/kg a.

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Hop Forms

• Whole Hops
• Hop Pellets
• CO2 Hop Extracts
• Isomerized Hop Pellets
• Isomerized Hop Extracts
• Reduced / Isomerized Hop Extracts
• Hop Resins / Hop Oils

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Hopping of World Beer Production2008 estimate
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Traditional Hop Types
Wort
Whole Hops
Wort
Hop Pellets
Wort
Hop Extracts
Beer
Dry Hop
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Advanced Hop Product Types
Isomerized Hop Pellets
Wort
Non-acidic resins and hop oils
Wort
Isomerized / Reduced Extracts
Wort
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Advanced Hop Product Types
Isomerized / Reduced Extracts
Beer
Beer
Hop Oils
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Traditional Hop Types
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Whole Hop Additions to Mashing

• Easily volatile and soluble hop oils are
  obtained, can also be obtained with more
  traditional hopping methods.
• Subtle hop character might be enzymatically
  released from glycoside bound components.
• Limited Iso-Alpha acids (soluble, already
  present).
• No alpha acids (insoluble, remain in spent
  grain).

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Whole Hop and Hop PelletHopping of Wort

• Bitter taste of beer
• Protein coagulation during wort boiling and
  influence beer character
• Typical hop character flavor and aroma of beer

• Solubilze and
• isomerize
• bittering substances
• Solution of polyphenols
• Hop oils

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Whole Hop and Hop Pellet Additions to the
Brewkettle

• Hop resins are released from the cones or
  pellets.
• The Alpha acids are converted to the Iso-Alpha
  acids (the bittering components in beer).
• Hop oils are solubilized, chemically changed or
  lost by evaporation.

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Whole Hops and Hop PelletsBitter Substances Loss
100 of bitterness
50 of bitterness
30 of bitterness
Whole Hops
Cold wort
Beer
50 loss
40 loss

• a not isomerized
• hot trub
• cold trub

• pH drop
• precipitation
• adsorbtion
• stabilization
• filtration

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Whole Hops and Hop PelletsAdvantages and
Disadvantages

• More traditional
• Solvent free
• Contribute to polyphenols
• BUT
• Loss of alpha and aroma on storage
• Lower bitterness utilization
• Variable - lot to lot / year to year
• Disposal of spent hops
• Bulky - expensive storage

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Hop Extracts

• Production Process
• Milling soft pelletizing
• Extraction with solvent
• Separation of solvent and hop extract
• Recovery of solvent from the hop extract
• Packaging of the extract

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Extract Solvents
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Supercritical CO2 Extraction
Typical Conditions Soft 2200 psi / 45oC Hard
4500 psi / 50oC
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Composition of CO2 Hop Extract
Alpha Acids 40 - 60 Beta Acids 15 - 45 Hop
Oils 2 - 10 Fats Waxes Trace Hard
Resins Trace Tannins Trace Water 1 - 5
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CO2 Hop ExtractAdvantages and Disadvantages

• Varietal identity, consistency - standardization
• Better product storage stability
• Reduced storage capacity required
• Improved bitterness utilization
• Reduced beer and wort losses
• Can have better economics than whole hops
• BUT
• / - polyphenols

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Isomerized Hop Pellets / ExtractsAdvantages and
Disadvantages

• Varietal identity
• Improved bitterness utilization
• BUT
• Addition of a catalyst, eg. Magnesium Oxide
• Process for isomerized pellets is to also heat at
  50oC for 10 days - can cause sweet, sulfury,
  cabbage, tobacco, solvent-like aromas

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HopsUtilization for Various Forms of Hops
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Advanced Hop ProductsApplications

• Advanced Hop Products are used for
• Precise control of bitterness
• Light-stability
• Beer foam enhancement
• Hop aroma and flavor
• Improved hop economy

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Advanced Hop Products
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Light-Struck Character Iso-alpha
AcidsLight-Struck Reaction
Arrow indicates weak bond, photo-sensitized to
form the acyl radical, which combines with
sulfur compounds causing the light-struck
reaction.
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Isomerized / Reduced Hop AcidsChemical Structure
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Isomerized / Reduced Hop AcidsChemical Structure
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Advanced Hop Products
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Advanced Hop Products
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Advanced Hop Products
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Advanced Hop Products
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Reduced and Isomerized ExtractsProcess
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Reduced and Isomerized ExtractsProcess
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Advanced Hop Character ProductsProcess
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Reduced and Isomerized Extracts Post-Fermentation
Addition

• Direct Injection
• Tank Addition

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Reduced and Isomerized Extracts Post-Fermentation
Addition

• Direct Injection
• Add prior to kieselguhr filter or final filter.
• Inject into the beer stream, preferably before a
  pump for better mixing.
• Preferable to design with the following criteria
• Use precise dosing equipment designed for low
  dosing rates.
• Dose hop acid proportional to beer flow.

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Reduced and Isomerized Extracts Post-Fermentation
Addition

• Tank Addition
• Add concentrated or diluted hop acid to empty
  maturation, pre-filtered beer or filtered beer
  tank.
• Add beer from the bottom to help disperse hop
  acids into solution.
• After tank is full, transfer to another empty
  beer tank for even better mixing.

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HopsHop Oils

• GC/MS analysis of hop oil fractions reveal 498
  discrete compounds in beer brewed with Hallertau
  Hersbrucker hops
• Monoterpenes, epoxides, alcohols and esters

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Hop Oil Components
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Hop Oil Components Hop Character Aroma and Flavor

• Hop varieties can be grouped into different
  categories with respect to aging
• Hop varieties which improve with aging.
• Hop varieties which lose hoppiness upon aging.
• Hop varieties which remain relatively unchanged
  with aging.

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Hop Oil ComponentsMajor Hydrocarbon Compounds

• ?-Pinene
• Myrcene
• ?-Caryophyllene
• Farnesene
• Humulene
• The major hydrocarbon hop oil compounds do not
  survive wort boil nor fermentation. However,
  these can be present in dry-hopped beers.

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Hydrocarbons based on GC/MS area
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Hop Oil ComponentsOxidation Product Compounds

• Caryophyllene Epoxide
• Humulene monoepoxide -I -II -III
• Humulene diepoxides -A -B -C
• Humulenol II
• Caryolan-1-ol (fenchyl alcohol)
• Nerolidol
• Some of the oxidation product hop oil compounds
  are thought to be noble aroma herbal, spicy

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Hop Oil Components Oxidation Product Compounds

• Oxidation products of ?-humulene are considered
  noble aroma hop compounds.
• Increasing oxidation products of ?-humulene
  requires a high level of ?-humulene in a hop
  variety that oxidizes at a reasonably steady
  state.

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Hop Oil ComponentsFloral and Citrus Compounds

• Floral Compounds
• Geranyl acetate
• Geranyl isobutyrate
• Geraniol
• Linalool
• The floral and citrus hop oil compounds
  contribute similar respective hop aroma and
  flavor character to beer.

• Citrus Compounds
• Limonene
• Citral
• Cadinene
• Nerol
• Limonen-10-ol

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Hop Oil Components Floral and Citrus Compounds

• Hop varieties high in citrus and floral compounds
  when fresh remain relatively the same after hops
  have aged.

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Aroma-Active Compounds Found in Four Hop
Varieties
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Magnum hops
100
95
Humulene
90
Myrcene
85
80
75
70
65
60
Caryophyllene
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Relative Abundance
50
45
40
35
30
25
20
15
10
5
0
0
5
10
15
20
25
30
Epoxides
Time (min)
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SBSE GC/MS - Aerated Wort
Internal STD carvone
Internal STD Carvacrol
Myrcene
Isoamyl isobutrate
Linalool
Geranyl acetate
epoxides
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SBSE GC/MS - Post Maturation
Octanoic Acid, ethyl ester
Hexanoic Acid, ethyl ester
Decanoic acid, ethyl ester
Phenyl ethyl Acetate
Internal STD carvone
Internal STD Carvacrol
Phenylethyl Alcohol
Linalool
epoxides
50
Headspace Samuel Adams
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Foam Layer of Samuel Adams
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Liquid Layer of Samuel Adams
RT
0.00 - 32.94
NL
36000000
3.61E7
TIC F c
34000000
Full ms
35.00-
32000000
250.00
MS liquidsa
30000000
3-methyl and 2-methyl 1-butanol acetate
28000000
Hexanoic Acid, ethyl ester
26000000
Twister
24000000
Octanoic Acid, ethyl ester
22000000
2,7-dimethyl-1,6-octadiene
20000000
Relative Abundance
3-methyl and 2 methyl 1-butanol
18000000
Phenyl ethyl Acetate
16000000
14000000
Phenylethyl Alcohol
12000000
Methyl4-methylhexa-2-enate Limonene
Isoamyl isobutyrate
10000000
Butanoic acid, ethyl ester
8000000
Decanoic acid
Dodcanoic Acid
6000000
Octanoic Acid
Linalool
4000000
2000000
0
epoxides
0
5
10
15
20
25
30
Time (min)
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Hop oil profile in hops is not the same hop
profile as in the final beer Difference in
kettle addition vs. post-fermentation
addition Use SBSE/Twister-GC/MS as an analysis
tool Use specially trained hop oil panel and
GC-O as a sensory tool
New Approach To Hop Oils
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Interdependence of bitterness, hop
character Focus is on Kettle hopping Limited
flexibility
Limitation of Traditional Hopping
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Break the linkage and independently
adjust Bitterness quality and intensity Light
stability Beer foam enhancement Hop Oil
Character Kettle dosing and Post-Fermentation
dosing
Consider The Possibilities
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Kettle Hop Bitterness Products Iso extracts for
bitterness Rho extracts for light-stable
bitterness
The Optimal Approach
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Kettle Hop Character Products Selected hop
resins and oils added to give background hop
character Hop resins with natural hop oil
components Augment or replace existing aroma
hops Wort foam suppression
The Optimal Approach
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Post-Fermentation Hop Bitterness Products Iso
extracts for bitterness Rho extracts for
light-stable bitterness Tetra extracts for
light-stable bitterness and beer foam
enhancement Hexa extracts for light-stable
bitterness beer foam enhancement and improved
mouth-feel
The Optimal Approach
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Post-Fermentation Hop Character
Products Selected natural hop oil components
added for distinctive hop character
The Optimal Approach
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HopsSpice of Beer

• Malted barley
• Cereal Grains
• Hops
• Water
• Yeast