啤酒风味稳定性 - 麦芽质量及制麦工艺控制点
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2012 9月17-18日 北京 (Beijing)
啤酒风味稳定性
1
麦芽 对 啤酒 风味 的 重要性
How important is malt to beer flavor
•剧情： 华 尔 街 时报 登载 手工 精 制 麦芽 将 种植 环境 纳入 啤酒 风格
Storyline: Craft malting is becoming a profession now in the USA.
9
EPR (电子顺磁共振) 测量抗氧化性
EPR(electron paramagnetic resonance) for measuring oxidative resistance
•分析啤酒氧化稳定性的标准方法 （ Beer-46 2009) 已被添加到 ASBC 分析 方法 A standard method (Beer-46 2009) for oxidative stability of beer has been added to the ASBC MOA (Methods Of Analysis) • 12 个实验室参加了方法的建立 12 labs participated the development work •原理基于对强制氧化过程 啤酒中自由 基生产的直接测量。Principle was based on direct measurement of free radical production in beer during a forced oxidation assay.
甜味/焦糖味及纸板味的形成机理中很多反应前体 来自麦芽 Many precursors for the last two mechanisms are from malt
啤酒风味稳定性与麦芽成分关系 Beer Flavor Stability and Malt
• 许多啤酒老化物的前体来源于大麦及制麦过程。
• 登场： 不 亚 于 葡萄酒 或香槟
Presentation: Barley to beer is like grapes to wine. So we can make beer a luxury on the dinner table too.
•尾声： 风味稳定性有待于 改进
Flavor Stability: However, in comparison with wine, the shelf-life of beer is an area of focus.
*Meilgaard, 1975; Ho, 1996
反应受二酮类催化/ 间接需要氧 Reaction catalysed by diketones / indirect need for O2 在啤酒中， 高温和高 ph 值(4.3-4.6) 益于反应 In beer, reaction favoured by high temperatures and high pH (4.3 - 4.6) 反应甚至在室温下瓶子里发生 May happen in the bottle even at room temperature
• 一些啤酒老化机制是通过自由基反应进行。
Some beer staling mechanisms are through free radical reaction
5
Change of LOX at different layers of the kiln bed
160 140 120 100 80 60 40 20 0 0 2
While cardboard flavor is due to the trans-2 nonenal formation from the degradation and oxidation of fatty acids, the toffee, sweet and caramel notes are more likely from the Strecker degradation of residual amino acids in the beer.
Many of the precursors of the beer stale compounds are originated from the barley and malting processes.
• 虽然纸板味形成的原因是由脂肪酸降解与氧化成反-2-壬烯醛， 但是太妃糖甜味和焦糖味特征更有可能是啤酒中残留氨基酸的 Strecker降解而至。
6
氨基酸降解及其Strecker醛风味化合物
Strecker Degradation of Amino-Acids and Resultant Flavor Compounds
氨基酸 Amino Acid 醛 Aldehyde 阈值 (PPM) Threshold Odor Characteristics
酿酒师谈风味稳定性
在 WBC 2012 会议上对不同麦芽啤酒样品的品尝调查
What brewers say about flavor stability
-Survey at WBC 2012 on beer made from control and test malt
I have a flavor stability issue in my brewery
发酵后不同程度的残留 氨基酸将为有关降解反应提供前体物质 Some formulations leave high levels of FAN at end of fermentation, which could serve as precursor for other undesirable reactions
- 麦芽质量及制麦工艺控制点
The Effect of Malt Quality and Malting Process on Beer Flavor Stability
尹象胜 Xiang S Yin 美国嘉吉麦芽公司 (Cargill Malt) 美国酿酒化学家协会(American Society of Brewing Chemists)
丙氨酸 Alanine 缬氨酸 Valine
CH3CHO (CH3)2CHCHO
10 (1.0)
辛辣、 青味、 甜 Pungent, green, sweet 辛辣、 青味、极低浓时果香味/香蕉味，极 易扩散 Pungent, green, fruity/banana @ v. low conc. Extremely diffusive 苦辛、极低浓时果香味/快感 Acrid-pungent, fruity/ pleasant @ v. low conc. 烘烤的可可或咖啡味，极低浓时果香味。 Roasted cocoa or coffee like. Fruity@ v. low conc. 极强、 辛辣、 花香、 甜味 Powerful, pungent, floral, sweet
99 151 130 46 52 111 490 178 17 134 14 13 356 2981 945
发酵第一天的第三组氨基酸的差异显著。氨基酸总残留水平与品种相关 ；有些是Strecker 反应的底物 Significant difference in group III on Day 1. Total residual level of AA is variety dependent; some are substrates for Strecker reaction, as marked by “ ”
7
商业化发酵过程中糖和游离氨基氮的同化走势
Patterns of Sugars and Free Amino Acid Uptake during Commercial Scale Fermentation
降糖曲线 Plato reduction
游离氨基氮 FAN reduction
Days of Fermentation
风味特征 Flavor 变化趋势 Trend during aging
苦味
果香/酯香 酒花香 涩味 纸板味
Bitterness
Fruity/Estery Hop Characters Astringency Papery/Cardboardy
酵母/硫化物 Yeasty/Sulphury 甜味/焦糖味 Sweetness/Caramel
Source: Yin, IGB Africa, 2001 8
发酵过程中的氨基酸的代谢程度
Amino Acid Metabolism during Fermentation
Harrington Histidine 267 Arginine 1042 Leucine 1044 Lysine 401 Subtotal-III crucial AA 2754 Glycine 129 Alanine 1145 Tyrosine 434 Valine 877 Isoleucine 492 Phenylalanine 681 Tryptophan 130 Subtotal-II important AA 3888 Aspartic Acid 88 Glutamic Acid 192 glutamine 362 Serine 579 Threonine 448 Methionine 189 Cysteine 60 Subtotal- others 1918 Proline 3323 Total AA, excl Pro 8560 Day 1 Fermentation Kendall Mecalfe 275 281 1103 795 1084 1074 408 418 2870 2568 130 143 1111 1061 465 477 855 836 485 494 701 688 122 124 3869 3823 68 66 181 166 342 338 615 653 455 465 203 194 70 1934 1882 3223 3199 8673 8273 Stratus 273 721 949 382 2325 100 1131 448 796 447 609 115 3646 72 198 314 555 536 188 36 1899 2501 7870 Harrington 58 41 Day 4 Fermentation Kendall Mecalfe 42 133 47 156 236 5 13 94 538 12 23 42 913 92 343 497 150 36 370 98 148 280 2444 181 181 22 24 92 299 56 40 14 14 25 16 15 381 598 3294 3460 755 3580 Stratus 120 147 188 11 466 18 828 259 425 131 294 128 2083 203 33 255 16 23 14 544 2455 3093
15% 3%
LOX-less beer tastes clearly fresher than control beer
55%
27%
3%
3% 5%
55% ： 本厂有风味稳定性问题
65% ： 测试麦芽啤酒风味明显稳定
24%
65%
在啤酒老化过程中风味变化趋势
Change in Flavor Profile during Beer Aging
上 层 Upper layer
Lox
中 层 Middle layer
底 层 Bottom layer
出炉麦芽 Malt L源自文库X：
4
Kiln time 干燥 时间 ( 小 时 )
6
8
11
13
off kiln
上层 Upper 2.2 底层 Bot. 0.8 中层 Mid 1.3
焙焦时间直接影响麦芽的平均LOX High heat does inactivate LOX, but the operational cost high
亮氨酸 Leucine 异亮氨酸 Isoleucine
(CH3)2CHCH2CHO CH3CH2CH(CH3)CHO
(0.6) 1.25
苯丙氨酸 Phenylalanine
C6H5CH2CHO
(1.6)
蛋氨酸 Methionine Ø Ø
Ø
CH3S.CH2CH2CHO
(0.25)
洋葱-肉汁、 熟土豆 Onion-meat-like, cooked potato
啤酒风味稳定性
1
麦芽 对 啤酒 风味 的 重要性
How important is malt to beer flavor
•剧情： 华 尔 街 时报 登载 手工 精 制 麦芽 将 种植 环境 纳入 啤酒 风格
Storyline: Craft malting is becoming a profession now in the USA.
9
EPR (电子顺磁共振) 测量抗氧化性
EPR(electron paramagnetic resonance) for measuring oxidative resistance
•分析啤酒氧化稳定性的标准方法 （ Beer-46 2009) 已被添加到 ASBC 分析 方法 A standard method (Beer-46 2009) for oxidative stability of beer has been added to the ASBC MOA (Methods Of Analysis) • 12 个实验室参加了方法的建立 12 labs participated the development work •原理基于对强制氧化过程 啤酒中自由 基生产的直接测量。Principle was based on direct measurement of free radical production in beer during a forced oxidation assay.
甜味/焦糖味及纸板味的形成机理中很多反应前体 来自麦芽 Many precursors for the last two mechanisms are from malt
啤酒风味稳定性与麦芽成分关系 Beer Flavor Stability and Malt
• 许多啤酒老化物的前体来源于大麦及制麦过程。
• 登场： 不 亚 于 葡萄酒 或香槟
Presentation: Barley to beer is like grapes to wine. So we can make beer a luxury on the dinner table too.
•尾声： 风味稳定性有待于 改进
Flavor Stability: However, in comparison with wine, the shelf-life of beer is an area of focus.
*Meilgaard, 1975; Ho, 1996
反应受二酮类催化/ 间接需要氧 Reaction catalysed by diketones / indirect need for O2 在啤酒中， 高温和高 ph 值(4.3-4.6) 益于反应 In beer, reaction favoured by high temperatures and high pH (4.3 - 4.6) 反应甚至在室温下瓶子里发生 May happen in the bottle even at room temperature
• 一些啤酒老化机制是通过自由基反应进行。
Some beer staling mechanisms are through free radical reaction
5
Change of LOX at different layers of the kiln bed
160 140 120 100 80 60 40 20 0 0 2
While cardboard flavor is due to the trans-2 nonenal formation from the degradation and oxidation of fatty acids, the toffee, sweet and caramel notes are more likely from the Strecker degradation of residual amino acids in the beer.
Many of the precursors of the beer stale compounds are originated from the barley and malting processes.
• 虽然纸板味形成的原因是由脂肪酸降解与氧化成反-2-壬烯醛， 但是太妃糖甜味和焦糖味特征更有可能是啤酒中残留氨基酸的 Strecker降解而至。
6
氨基酸降解及其Strecker醛风味化合物
Strecker Degradation of Amino-Acids and Resultant Flavor Compounds
氨基酸 Amino Acid 醛 Aldehyde 阈值 (PPM) Threshold Odor Characteristics
酿酒师谈风味稳定性
在 WBC 2012 会议上对不同麦芽啤酒样品的品尝调查
What brewers say about flavor stability
-Survey at WBC 2012 on beer made from control and test malt
I have a flavor stability issue in my brewery
发酵后不同程度的残留 氨基酸将为有关降解反应提供前体物质 Some formulations leave high levels of FAN at end of fermentation, which could serve as precursor for other undesirable reactions
- 麦芽质量及制麦工艺控制点
The Effect of Malt Quality and Malting Process on Beer Flavor Stability
尹象胜 Xiang S Yin 美国嘉吉麦芽公司 (Cargill Malt) 美国酿酒化学家协会(American Society of Brewing Chemists)
丙氨酸 Alanine 缬氨酸 Valine
CH3CHO (CH3)2CHCHO
10 (1.0)
辛辣、 青味、 甜 Pungent, green, sweet 辛辣、 青味、极低浓时果香味/香蕉味，极 易扩散 Pungent, green, fruity/banana @ v. low conc. Extremely diffusive 苦辛、极低浓时果香味/快感 Acrid-pungent, fruity/ pleasant @ v. low conc. 烘烤的可可或咖啡味，极低浓时果香味。 Roasted cocoa or coffee like. Fruity@ v. low conc. 极强、 辛辣、 花香、 甜味 Powerful, pungent, floral, sweet
99 151 130 46 52 111 490 178 17 134 14 13 356 2981 945
发酵第一天的第三组氨基酸的差异显著。氨基酸总残留水平与品种相关 ；有些是Strecker 反应的底物 Significant difference in group III on Day 1. Total residual level of AA is variety dependent; some are substrates for Strecker reaction, as marked by “ ”
7
商业化发酵过程中糖和游离氨基氮的同化走势
Patterns of Sugars and Free Amino Acid Uptake during Commercial Scale Fermentation
降糖曲线 Plato reduction
游离氨基氮 FAN reduction
Days of Fermentation
风味特征 Flavor 变化趋势 Trend during aging
苦味
果香/酯香 酒花香 涩味 纸板味
Bitterness
Fruity/Estery Hop Characters Astringency Papery/Cardboardy
酵母/硫化物 Yeasty/Sulphury 甜味/焦糖味 Sweetness/Caramel
Source: Yin, IGB Africa, 2001 8
发酵过程中的氨基酸的代谢程度
Amino Acid Metabolism during Fermentation
Harrington Histidine 267 Arginine 1042 Leucine 1044 Lysine 401 Subtotal-III crucial AA 2754 Glycine 129 Alanine 1145 Tyrosine 434 Valine 877 Isoleucine 492 Phenylalanine 681 Tryptophan 130 Subtotal-II important AA 3888 Aspartic Acid 88 Glutamic Acid 192 glutamine 362 Serine 579 Threonine 448 Methionine 189 Cysteine 60 Subtotal- others 1918 Proline 3323 Total AA, excl Pro 8560 Day 1 Fermentation Kendall Mecalfe 275 281 1103 795 1084 1074 408 418 2870 2568 130 143 1111 1061 465 477 855 836 485 494 701 688 122 124 3869 3823 68 66 181 166 342 338 615 653 455 465 203 194 70 1934 1882 3223 3199 8673 8273 Stratus 273 721 949 382 2325 100 1131 448 796 447 609 115 3646 72 198 314 555 536 188 36 1899 2501 7870 Harrington 58 41 Day 4 Fermentation Kendall Mecalfe 42 133 47 156 236 5 13 94 538 12 23 42 913 92 343 497 150 36 370 98 148 280 2444 181 181 22 24 92 299 56 40 14 14 25 16 15 381 598 3294 3460 755 3580 Stratus 120 147 188 11 466 18 828 259 425 131 294 128 2083 203 33 255 16 23 14 544 2455 3093
15% 3%
LOX-less beer tastes clearly fresher than control beer
55%
27%
3%
3% 5%
55% ： 本厂有风味稳定性问题
65% ： 测试麦芽啤酒风味明显稳定
24%
65%
在啤酒老化过程中风味变化趋势
Change in Flavor Profile during Beer Aging
上 层 Upper layer
Lox
中 层 Middle layer
底 层 Bottom layer
出炉麦芽 Malt L源自文库X：
4
Kiln time 干燥 时间 ( 小 时 )
6
8
11
13
off kiln
上层 Upper 2.2 底层 Bot. 0.8 中层 Mid 1.3
焙焦时间直接影响麦芽的平均LOX High heat does inactivate LOX, but the operational cost high
亮氨酸 Leucine 异亮氨酸 Isoleucine
(CH3)2CHCH2CHO CH3CH2CH(CH3)CHO
(0.6) 1.25
苯丙氨酸 Phenylalanine
C6H5CH2CHO
(1.6)
蛋氨酸 Methionine Ø Ø
Ø
CH3S.CH2CH2CHO
(0.25)
洋葱-肉汁、 熟土豆 Onion-meat-like, cooked potato