ALCOHOL L SCHOOL

DISTILLAT ATION AND MOLECULA AR SIEVES: A PRACTICAL VIEWPOINT

Cincinnati, Ohio U S A

Philip W. . Madson President

FUNDAM MENTALS O OF DISTILL LATION

TYPICAL DI ISTILLATION RELATIO ONSHIPS

VAPOUR LOWER TEMPERATURE REFLUX LIQUID FEED
`

CONDENSER COOLING WATER OVERHEAD PRODUCT

TRAYS (CONTACTING DEVICES)

THERMAL ENERGY HIGHER TEMPERATURE

VAPOUR BOILING LIQUID

BOTTOMS PROD DUCT

VAPOUR-LIQUID VAPOURD EQUILIBRIUM ETHANOL L-WATER

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

MOLE % ET THANOL IN LIQUID

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

AZEOTROPE 194.4 PROOF

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

AZEOTROPE 194.4 PROOF

100 90

EQUILIBRIUM CURVE

80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

STRUCTURING TH HE DISTILLATION SYSTEM STRATEGY S

STRIPPING SYST TEM RECTIFYING G SYSTEM

100 90

DEHYDRATION SYSTEM ANHYDROUS PRODUCT AZEOTROPE 194.4 PROOF SPIRIT

EQUILIBRIUM CURVE

80 70

MOLE % ETHANOL IN VAPOUR

60 50 40 30 20 10 0

(10 VOLUME % FEED)

0 10 20 30 40 50 60 70 80 90 100

STILLAGE

MOLE % ETH HANOL IN LIQUID

OPERATI ING LINE

Locus of possible co oncentrations of liquid and vapour passing p in tower for a given energy inpu ut

100

EQUILIBRIUM CURVE
80 70 60

90

AZEOTROPE 190 PROOF SPIRIT

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0

OP PERATING LINE ST TRIPPING TYPICAL L L/V = 5.0

0 STILLAGE (0.02 WT. %) BEER FEED (10 VOLUME %)

10

20

30

40

50

60

70

80

90

100

MOLE % ETHANOL IN LIQUID

100

EQUILIBRIUM CURVE
80 70 60

90

AZEOTROPE 190 PROOF SPIRIT

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0

OPERATING LINE RECTIFYING

0 STILLAGE (0.02 WT. %) BEER FEED (10 VOLUME %)

10

20

30

40

50

60

70

80

90

100

MOLE % ETHANOL IN LIQUID

100

EQUILIBRIUM CURVE
80 70 60

90

AZEOTROPE 190 PROOF SPIRIT

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0

OPERATING LINE RECTIFYING OP PERATING LINE ST TRIPPING TYPICAL L L/V = 5.0

0 STILLAGE (0.02 WT. %) BEER FEED (10 VOLUME %)

10

20

30

40

50

60

70

80

90

100

MOLE % ETHANOL IN LIQUID

VAPOUR-LIQUID VAPOURD EQUILIBRIUM STAGE ANALYSIS A

TYPICAL - 14 REC CTIFYING STAGES - 8 STR RIPPING STAGES

100

EQUILIBRIUM CURVE
80 70 60 4 3 2

90

1213 8 9 10 11 12 1314 14

7 5 6

AZEOTROPE 190 PROOF SPIRIT

MOLE % ETHANOL IN VAPOUR

50 40 30 1 20 10 0

OPERATING LINE RECTIFYING OP PERATING LINE ST TRIPPING TYPICAL L L/V = 5.0

0 STILLAGE (0.02 WT. %) BEER FEED (10 VOLUME %)

10

20

30

40

50

60

70

80

90

100

MOLE % ETHANOL IN LIQUID

VAPOUR-LIQUID VAPOURD EQUILIBRIUM STAGE A ANALYSIS

100 90

8 9 10 11 12 13 14

MOLE % ETHANOL IN VAPOUR

TYPICAL - 14 RECTIFYING STAGES - 8 STRIPPING STAGES
8 9 10 11121314 7 5 6 4 3 60 50 40 30 20 10 0 2

80

70

4 3

7 6 5

190 PROOF SPIRIT

100 90 80 70

60
190 PROOF SPIRIT

EQUILIBRIUM CURVE

OPERATING LINE RECTIFICATION OPERATING LINE STRIPPING TYPICAL L/V = 5.0

40

50

OPERATING LINE RECTIFYING

STILLAGE (0.02 WT. %)

10

20

30

50

60

70

80

90

100

BEER FEED (10 VOLUME %)

MOLE % ETHANOL IN LIQUID

40

50

60

70

80

90

100

MOLE % ETHANOL IN LIQUID

VAPOUR-LIQUID VAPOURD EQUILIBRIUM STAGE ANALYSIS A

30

MOLE % 20 ETHANOL 1 IN VAPOUR

100 90 80 70 3 60 50 40 30 20 10 0 2

OPERATING LINE STRIPPING TYPICAL L/V = 5.0 BEER FEED (10 VOLUME %)

TYPICAL - 14 RECTIFYING STAGES - 8 STRIPPING STAGES

8 9 10 11121314 7 5 6 4

2 10
190 PROOF SPIRIT

EQUILIBRIUM CURVE

OPERATING LINE RECTIFICATION OPERATING LINE STRIPPING TYPICAL L/V = 5.0

40

8
80 90 100

STILLAGE (0.02 WT. %)

10

20

30

50

60

70

BEER FEED (10 VOLUME %)

MOLE % ETHANOL IN LIQUID

STILLAGE (0.02 WT. %)

0 0 10 20 30 40

M MOLE % ETHANOL IN LIQUID

DISTILLATIO ON ENERGY CONSUM MPTION

STEAM REQ QUIREMENTS ETHANOL STRIP PPERPPER -RECTIFIER

50 45 40

BTU (In 1000s) PER GALLON ETHANOL (ANHYDROUS BASIS)

35 30 25 20 15 10 5 0 0 5 10 15 CONSTRAINTS: 190 PROOF PRODUCT 0.02% (WT.) BOTTOMS SATURATED FEED

BEER CONC CENTRATION (VOLU UME %)

12 11 10 9

MJ PER LITER ETHANOL (ANHYDROUS BASIS)

8 7 6 5 4 3 2 1 0 0 5 10 15
CONSTRAINTS: 190 PROOF PRODUCT 0.02% (WT.) BOTTOMS SATURATED FEED

BEER CONC CENTRATION (VOLU UME %)

ENE ERGY EFFICI IENCY

TRADIT TIONAL
VAPOUR REFLUX CW CONDENSER VAPOUR REFLUX CW CONDENSER

FEED

OVERHEAD PRODUCT

FEE ED

OVERHEAD PRODUCT

STEAM (ENERGY)

TOWER 1

STE EAM (EN NERGY)

TOWER 2

BOTTOMS PRODUCT

BOTTOMS PRODUCT

Energy Ineffic cient

ENERGY TR RANSFER BY FORCED - CI IRCULATION REBO OILER

CONDENSER VAPOUR RE ECTIFYIN NG REFLUX COOLING WATER LOW- BOILING LOWPRODUCT

FEED MIXTURE STEAM (ENERGY) REBOILER CONDENSATE RETURN TO BOILER

S STRIPPIN NG

HIGH - BOILING PRODUCT

ONE - LEVEL ENERGY CASC CADE

ENERGY CASCADE
CONDENSER VAPOUR REFLUX VAPOUR REFLUX OVERHEAD PRODUCT

FEED

FEED

STEAM (ENERGY)

TOWER 1

RE ECOVERED ENERGY REBOILER

TOWER 2

BOTTOMS PRODUCT

OVERHEAD PRODUCT

BOTTOMS PRODUCT

ENERGY CASCADE E - FEED PREHEAT

VAPOUR VAPOUR FEED REFLUX CONDENSER

REFLUX HOT FEED

FEED

OVERHEAD PRODUCT

STEAM (ENERGY)

TOWER 1

RE ECOVERED ENERGY REBOILER

TOWER 2

BOTTOMS PRODUCT

OVERHEAD PRODUCT

BOTTOMS PRODUCT

TWO - LEVEL ENERGY CASC CADE (3 TO OWER)

50 45 40

BTU (In 1000s) PER GALLON ETHANOL (ANHYDROUS BASIS)

35 30 25 20 15 10 5 0 0 5 10 15 CONSTRAINTS: 190 PROOF PRODUCT 0.02% (WT.) BOTTOMS SATURATED FEED

BEER CONC CENTRATION (VOLU UME %)

12 11 10 9

MJ PER LITER ETHANOL (ANHYDROUS BASIS)

8 7 6 5 4 3 2 1 0 0 5 10 15
CONSTRAINTS: 190 PROOF PRODUCT 0.02% (WT.) BOTTOMS SATURATED FEED

BEER CONC CENTRATION (VOLU UME %)

ENE ERGY REQUIRE EMENTS

BASIC

StrippingStripping pp g-Co oncentrating g

14 lb STEAM per U.S S. GALLON (absolute) o or 1.7 Kg g STEAM M per LITER

ENE ERGY REQUIRE EMENTS

ADVANCED-INTEGRATED

StrippingStripping pp g-Co oncentrating g

9 lb STEAM per U.S. . GALLON (absolute) o or 1.1 Kg g STEAM M per LITER

CONTACTIN NG DEVICES (TRA ( AYS) )

DISTILLATION TR RAY FUNCTIONS

MIX RISING VAPOUR WITH FA ALLING LIQUID ALLOW FOR SEPARATION AFT TER MIXING PROVIDE PATH FOR LIQUID TO T PROCEED DOWN THE TOWER PROVIDE PATH FOR VAPOUR TO PROCEED UP THE TOWER

ENRICHE ED VAPOUR LIQUID

V-L MIXING

STRIPPED LIQUID

VAPOUR

PERFORA ATED TRAYS

OUTLET WEIR INLET WEIR

DOWNCOMER AREA

DOWNCOMING LIQUID ENRICHED VAPOUR

V-L SEPARATION V-L MIXING

VAPOUR

STRIPPED LIQUID

PERFORATED TRAY T FROTHING

OUTLET WEIR IN NLET WEIR ENRICHED VAPOUR DOWNCOMER AREA FRO OTH ZONE DOWNCOMING LIQUID

V-L SEPARATION

V-L MIXING

VAPOUR STRIPPED LIQUID

RELIAB BILITY
BEER ST TRIPPER FOUL LING

DISCDISC -DONU UT TRAYS

DON NUTS DESCENDING LIQUID DISC DESCENDING LIQUID

ENRICHED VAPOUR

VAPOUR

STRIPPED STILLAGE

Bacardi Baca rdi

DISCDISC -DONU UT TRAYS

DON NUTS DESCENDING LIQUID DISC DESCENDING LIQUID

ENRICHED VAPOUR

FOULING

VAPOUR

STRIPPED STILLAGE

PERFORA ATED TRAYS

OUTLET WEIR INLET WEIR

DOWNCOMER AREA

DOWNCOMING LIQUID ENRICHED VAPOUR

FOULIN NG VAPOUR STRIPPED LIQUID

BAFFLE - TRAY Y EXPERIENCE

39 COMMERCIAL SYSTEMS S
- SULFITE PULPING LIQUO OR - FERMENTED SULFITE LI IQUOR - FERMENTED LIGNOLIGNO IGNO-CEL CELLULOSE U OSE HYDROLYZATE HYDRO YZATE - FERMENTED WHOLE GR RAIN - ALCELL PULPING LIQUO OR - FERMENTED CHEESE WHEY W - FERMENTED CANE MOL LASSES

BAFFLE - TRAY Y EXPERIENCE

5 YEAR CLEAN NING CYCLE FERMENTED GRAIN G 1 YEAR CLEAN NING CYCLE FERMENTED CHEESE C WHEY ELIMINATED ANTI A ANTI-FOAM AND ANTIANTISCALANT 6-12 MONTH CLEANING C CYCLE FERMENTED C MOLASSES

RECOMMENDED TRAY DESIGNS

BEERSTILLS (ALL FOULING FEED DSTOCKS) - BAFFLE TRAY RECTIFIERS EXTRACTIVE TOWERS TECHNICAL ALCOHOL TOWERS - PERFORATED TRAY - PERFORATED TRAY - PERFORATED TRAY - PACKED ( < 24 )

CONT CO TROL O STRAT TEGIES

TEMPERATURE AND D PROOF PROFILE

CONDENSER REFLUX PRODUCT (190 PROOF SPIRITS) TEMPERATURE
TOP TRAY RECTIFIER

PROOF ZONE OF CONTROL

BEER FEED
STRIPPER BOTTOM TRAY

TEMP. (C) 77 77 77 78 78 79 80 84 85 93 98 102 106 106 107 107 107

GL 95 94.5 94 93 91 5 91.5 89 84 75 69 60 40 20 5 1.5 0.5 0.005 0.00005

STILLAGE

STEAM

TEMPERATURE AND D PROOF PROFILE

CONDENSER REFLUX PRODUCT (190 PROOF SPIRITS) TEMPERATURE
TOP TRAY RECTIFIER

PROOF ZONE OF CONTROL

BEER FEED
STRIPPER BOTTOM TRAY

TEMP. (F) 170 170 171 172 173 174 176 184 191 199 208 216 222 223 224 225 225

PR. (U.S.) 190 189 188 186 183 178 168 150 138 120 80 40 10 3 1 0.01 0.0001

STILLAGE

STEAM

190 PROOF SPIRITS

FC

BEER FEED

TC FC

CONDENSER

STEAM

FC LC LC

REFLUX DRUM

STILLAGE

STRIPPE ERER RECTIFI IER

DEHYDR RATION RATION

VAPOUR-LIQUID VAPOURD EQUILIBRIUM ETHANOL L-WATER

AZEOTROPE 194.4 PROOF

100 90

EQUILIBRIUM CURVE

80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10 0 0 10 20 30 4 40 50 60 70 80 90 100

(10 VOLUM ME % FEED)

MOLE % ET THANOL IN LIQUID

STRUCTURING TH HE DISTILLATION SYSTEM STRATEGY S

STRIPPING SYST TEM RECTIFYING G SYSTEM

100 90

DEHYDRATION SYSTEM ANHYDROUS PRODUCT AZEOTROPE 194.4 PROOF SPIRIT

EQUILIBRIUM CURVE

80 70

MOLE % ETHANOL IN VAPOUR

60 50 40 30 20 10 0

(10 VOLUME % FEED)

0 10 20 30 40 50 60 70 80 90 100

STILLAGE

MOLE % ETH HANOL IN LIQUID

TERN NARY AZEOT TROPE DEHYDR RATION O

ANHYDROUS ETH HANOL SYSTEM

ANHYDROUS ETHANOL 190 PROOF ETHANOL FEED
STEAM CONDENSATE D DECANTER WASTE WATER

DEHYDRATION TOWER

ENTRAINER TOWER

MOLECUL LAR SIEVE DEHYDR RATION

VAPOUR PHASE ADSORPTION NO ENTRAINE ER LOW ENERGY Y

MOLECULA AR SIEVE TYPE E 3A

CHEMICAL FORMULA: (K2O Na2O) Al2O3 2SiO2 XH2O

Molecular Sieve Media Type 3A

O H H

H H H O H C C H H

H H H H O H C C H H H O H O H H H H O H C C H H H O H C C H H H H H H O H H H C C H H H H H O H C C H

MOLECULAR SIEVE BED

INTERMEDIATE SUPPORT ADSORBENT BED INTERMEDIATE SUPPORT SUPPORT MEDIUM

MFGE DISTILLATION N & DEHYDRATION PSA MOLECULAR SIEVE

BEER FEED
STEAM

MFGE PRODUCT

RECTIFIER BEER STRIPPER

REBOILER STM. COND. REBOILER WATER

DEHYDRATION BEDS A B

FUS SEL OIL DEC CANTER ST TEAM COND. REBOILER

VACUUM PUMP

STILLAGE

WATER

Mahi ildra ildra

LAI ICA ICA

DISTILLATIONDISTILLATION -DEHYDRATION TECHNOLOGY

TYPE
1970s STANDALONE 1980s INTEGRATED COMPLEX 1990s INTEGRATED USER FRIENDLY 2000s ADDITIONAL INTEGRATION

DEHYD DRATION TECHN NOLOGY

AZEO OTROPIC AZEO OTROPIC MOLE ECULAR SIEVE E

ENERGY (MJ/L) (BTU/Gal) (BTU/G l)

9.5 4.7 3.9 34,000 17,000 14,000