DISTILLATION AND MOLECULAR SIEVES: A PRACTICAA PRACTICAL

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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 DIISTILLATION RELATIO ONSHIPS CONDENSER

VAPOUR LOWER TEMPERATURE

COOLING WATER REFLUX LIQUID

FEED `

THERMAL ENERGY HIGHER TEMPERATURE

VAPOUR BOILING LIQUID

BOTTOMS PROD DUCT

OVERHEAD PRODUCT

TRAYS (CONTACTING DEVICES)

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

MOLE % ET THANOL IN LIQUID

100

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

AZEOTROPE 194.4 PROOF 100 90 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

AZEOTROPE 194.4 PROOF 100 90

EQUILIBRIUM CURVE

80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30 20 10

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

STRUCTURING TH HE DISTILLATION SYSTEM STRATEGY S

STRIPPING SYST TEM

DEHYDRATION SYSTEM ANHYDROUS PRODUCT

RECTIFYING G SYSTEM 100 90

EQUILIBRIUM CURVE

AZEOTROPE 194.4 PROOF

80 70

MOLE % ETHANOL IN VAPOUR

SPIRIT

60 50 40 30 20 10

(10 VOLUME % FEED)

0

STILLAGE

0

10

20

30

40

50

60

70

80

90

100

MOLE % ETH HANOL IN LIQUID

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

100 90

AZEOTROPE 190 PROOF SPIRIT

EQUILIBRIUM CURVE 80 70 60

MOLE % ETHANOL IN VAPOUR

50 40 30

OP PERATING LINE ST TRIPPING

20

TYPICAL L L/V = 5.0

10 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 90

AZEOTROPE 190 PROOF SPIRIT

EQUILIBRIUM CURVE 80 70 60

MOLE % ETHANOL IN VAPOUR

50

OPERATING LINE RECTIFYING

40 30 20 10 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 90

AZEOTROPE 190 PROOF SPIRIT

EQUILIBRIUM CURVE 80 70 60

MOLE % ETHANOL IN VAPOUR

50

OPERATING LINE RECTIFYING

40 30

OP PERATING LINE ST TRIPPING

20

TYPICAL L L/V = 5.0

10 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 90

1213 8 9 10 11 12 1314 14

80

7 5 6

EQUILIBRIUM CURVE 4

70

AZEOTROPE 190 PROOF SPIRIT

3

60

MOLE % ETHANOL IN VAPOUR

2

50

OPERATING LINE RECTIFYING

40 30 1

OP PERATING LINE ST TRIPPING

20

TYPICAL L L/V = 5.0

10 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

MOLE % ETHANOL IN VAPOUR

90

8 9 10 11 12 13 14

80

7 6 5

4

70

190 PROOF SPIRIT

3 60

TYPICAL - 14 RECTIFYING STAGES - 8 STRIPPING STAGES

100 90

OPERATING LINE RECTIFYING

8 9 10 11121314

EQUILIBRIUM CURVE 80

7 5 6

190 PROOF SPIRIT

4

70 3 60 2

50

OPERATING LINE RECTIFICATION

40 30

50

OPERATING LINE STRIPPING TYPICAL L/V = 5.0

1

20 10 0

STILLAGE (0.02 WT. %)

0

10

20

30

40

50

60

70

80

90

100

BEER FEED (10 VOLUME %)

MOLE % ETHANOL IN LIQUID

40

50

60

70

80

90

MOLE % ETHANOL IN LIQUID

100

VAPOUR-LIQUID VAPOURD EQUILIBRIUM STAGE ANALYSIS A 30

OPERATING LINE STRIPPING

MOLE % 20 ETHANOL 1 IN VAPOUR 2 10

TYPICAL - 14 RECTIFYING STAGES - 8 STRIPPING STAGES

100 90

8 9 10 11121314

80

7 5 6

EQUILIBRIUM CURVE

190 PROOF SPIRIT

4

70 3 60 2

50

OPERATING LINE RECTIFICATION

40 30

8

OPERATING LINE STRIPPING TYPICAL L/V = 5.0

1

20 10 0

STILLAGE (0.02 WT. %)

0

10

20

30

40

50

60

70

80

90

100

BEER FEED (10 VOLUME %)

MOLE % ETHANOL IN LIQUID

TYPICAL L/V = 5.0

7

6

5

STILLAGE (0.02 WT. %)

4

BEER FEED (10 VOLUME %)

3

0 0

10

20

30

40

M MOLE % ETHANOL IN LIQUID

DISTILLATIO ON ENERGY CONSUM MPTION

STEAM REQ QUIREMENTS ETHANOL STRIP PPER--RECTIFIER PPER

50 45 40

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

35 30 25 20 15 10 5 0 0

5

10

BEER CONC CENTRATION (VOLU UME %)

15 CONSTRAINTS: • 190 PROOF PRODUCT • 0.02% (WT.) BOTTOMS • SATURATED FEED

12 11 10 9

MJ PER LITER ETHANOL (ANHYDROUS BASIS)

8 7 6 5 4 3 2 1 0 0

5

BEER CONC CENTRATION (VOLU UME %)

10

15 CONSTRAINTS: • 190 PROOF PRODUCT • 0.02% (WT.) BOTTOMS • SATURATED FEED

ENE ERGY EFFICIIENCY

TRADIT TIONAL CW

VAPOUR REFLUX

CONDENSER

OVERHEAD PRODUCT

FEED

STEAM (ENERGY)

TOWER 1

BOTTOMS PRODUCT

CW

VAPOUR REFLUX

CONDENSER

OVERHEAD PRODUCT

FEE ED

STE EAM (EN NERGY)

TOWER 2

BOTTOMS PRODUCT

Energy Ineffic cient

ENERGY TR RANSFER BY FORCED - CIIRCULATION REBO OILER

CONDENSER

FEED

RE ECTIFYIN NG

VAPOUR

COOLING WATER REFLUX

LOW- BOILING LOWPRODUCT

STEAM (ENERGY)

S STRIPPIN NG

MIXTURE

REBOILER CONDENSATE RETURN TO BOILER

HIGH - BOILING PRODUCT

ONE - LEVEL ENERGY CASC CADE

ENERGY CASCADE CONDENSER VAPOUR

VAPOUR

REFLUX

REFLUX

FEED

FEED

STEAM (ENERGY)

TOWER 1

RE ECOVERED ENERGY

OVERHEAD PRODUCT

TOWER 2

REBOILER BOTTOMS PRODUCT

OVERHEAD PRODUCT

BOTTOMS PRODUCT

ENERGY CASCADE E - FEED PREHEAT VAPOUR

VAPOUR

REFLUX

REFLUX HOT FEED

STEAM (ENERGY)

FEED

FEED

TOWER 1

RE ECOVERED ENERGY

OVERHEAD PRODUCT

TOWER 2

REBOILER BOTTOMS PRODUCT

OVERHEAD PRODUCT

CONDENSER

BOTTOMS PRODUCT

TWO - LEVEL ENERGY CASC CADE (3 – TO OWER)

50 45 40

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

35 30 25 20 15 10 5 0 0

5

10

BEER CONC CENTRATION (VOLU UME %)

15 CONSTRAINTS: • 190 PROOF PRODUCT • 0.02% (WT.) BOTTOMS • SATURATED FEED

12 11 10 9

MJ PER LITER ETHANOL (ANHYDROUS BASIS)

8 7 6 5 4 3 2 1 0 0

5

BEER CONC CENTRATION (VOLU UME %)

10

15 CONSTRAINTS: • 190 PROOF PRODUCT • 0.02% (WT.) BOTTOMS • SATURATED FEED

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

DOWNCOMER AREA

INLET WEIR

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

DOWNCOMING LIQUID

FRO OTH ZONE

V-L SEPARATION

V-L MIXING

VAPOUR STRIPPED LIQUID

RELIAB BILITY BEER ST TRIPPER FOUL LING

DISC--DONU DISC UT TRAYS DON NUTS DESCENDING LIQUID DISC

DESCENDING LIQUID

ENRICHED VAPOUR

VAPOUR

STRIPPED STILLAGE

Bacardi Baca rdi

DISC--DONU DISC UT TRAYS DON NUTS DESCENDING LIQUID DISC

DESCENDING LIQUID

ENRICHED VAPOUR

FOULING

VAPOUR

STRIPPED STILLAGE

PERFORA ATED TRAYS OUTLET WEIR

INLET WEIR

DOWNCOMING LIQUID ENRICHED VAPOUR

DOWNCOMER AREA

FOULIN NG VAPOUR

STRIPPED LIQUID

BAFFLE - TRAY Y EXPERIENCE • 39 COMMERCIAL SYSTEMS S - SULFITE PULPING LIQUO OR - FERMENTED SULFITE LIIQUOR - 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

- PERFORATED TRAY

EXTRACTIVE TOWERS

- PERFORATED TRAY

TECHNICAL ALCOHOL TOWERS

- PERFORATED TRAY - PACKED ( < 24” )

CONT CO TROL O STRAT TEGIES

TEMPERATURE AND D PROOF PROFILE CONDENSER REFLUX PRODUCT (190 PROOF SPIRITS)

TOP TRAY RECTIFIER

PROOF

TEMPERATURE

ZONE OF CONTROL BEER FEED STRIPPER

STILLAGE

BOTTOM TRAY

STEAM

TEMP. (°C) 77 77 77 78 78 79 80 84 85 93 98

°GL 95 94.5 94 93 91 5 91.5 89 84 75 69 60 40

102 106 106 107 107 107

20 5 1.5 0.5 0.005 0.00005

TEMPERATURE AND D PROOF PROFILE CONDENSER REFLUX PRODUCT (190 PROOF SPIRITS)

TOP TRAY RECTIFIER

PROOF

TEMPERATURE

ZONE OF CONTROL BEER FEED STRIPPER

STILLAGE

BOTTOM TRAY

STEAM

TEMP. (°F) 170 170 171 172 173 174 176 184 191 199 208

°PR. (U.S.) 190 189 188 186 183 178 168 150 138 120 80

216 222 223 224 225 225

40 10 3 1 0.01 0.0001

190 PROOF SPIRITS

BEER FEED

STEAM

FC

CONDENSER

TC FC

FC LC

STILLAGE

STRIPPE ER-ER RECTIFIIER

LC

REFLUX DRUM

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

(10 VOLUM ME % FEED)

0 0

10

20

30

4 40

50

60

70

80

90

MOLE % ET THANOL IN LIQUID

100

STRUCTURING TH HE DISTILLATION SYSTEM STRATEGY S

STRIPPING SYST TEM

DEHYDRATION SYSTEM ANHYDROUS PRODUCT

RECTIFYING G SYSTEM 100 90

EQUILIBRIUM CURVE

AZEOTROPE 194.4 PROOF

80 70

MOLE % ETHANOL IN VAPOUR

SPIRIT

60 50 40 30 20 10

(10 VOLUME % FEED)

0

STILLAGE

0

10

20

30

40

50

60

70

80

90

100

MOLE % ETH HANOL IN LIQUID

TERN NARY AZEOT TROPE DEHYDR RATION O

ANHYDROUS ETH HANOL SYSTEM ANHYDROUS ETHANOL 190 PROOF ETHANOL FEED STEAM D DECANTER

CONDENSATE

DEHYDRATION TOWER

WASTE WATER

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

C

H

O

C H

H

H H

H H H

H C

C

H

O

H

O

C

C H H

O

H

H

H H

H

O

H H

H

C

H

H

O

H H

C

C

H

O

H

C

H H

H

H

H

H

C

H

O

C H

H

H

MOLECULAR SIEVE BED

INTERMEDIATE SUPPORT ADSORBENT BED INTERMEDIATE SUPPORT SUPPORT MEDIUM

MFGE DISTILLATION N & DEHYDRATION PSA MOLECULAR SIEVE MFGE

BEER FEED

PRODUCT

STEAM

RECTIFIER BEER STRIPPER REBOILER

WATER

REBOILER

STM. COND.

STILLAGE

FUS SEL OIL DEC CANTER ST TEAM COND. REBOILER

WATER

DEHYDRATION BEDS A B

VACUUM PUMP

Mahiildra ildra

LAIICA ICA

DISTILLATION--DEHYDRATION DISTILLATION TECHNOLOGY TYPE

DEHYD DRATION TECHN NOLOGY

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

1970’s STANDALONE

AZEO OTROPIC

9.5

34,000

1980’s INTEGRATED COMPLEX

AZEO OTROPIC

4.7

17,000

1990’s INTEGRATED USER FRIENDLY

MOLE ECULAR SIEVE E

3.9

14,000

2000’s ADDITIONAL INTEGRATION