LOW ENERGY D I S T I L L A T I O N SYSTEMS

R . Katzen, W . R .

Ackley,

G.D. Moon, J r . ,

J.R.

Messick, B.F.

B r u s h , K . F . Kaupisch

Raphael Katzen Associates International, I n c . 1050 Delta Avenue, Cincinnati, Ohio 45208

ABSTRACT Much work, aimed a t improvements in t h e manufacture and r e c o v e r y e t h y l alcohol, i s c u r r e n t l y being conducted in connection w i t h t h e p r o d u c t i o n o f s u b s t i t u t e liquid fuels; e..g., Gasohol. A p r i m a r y c o n s i d e r ation in all schemes f o r p r o d u c i n g s u b s t i t u t e liquid f u e l s lies in t h e e n e r g y consumed t o p r o d u c e t h e fuels. B y e n e r g y re-use, p r e s s u r e cascading a n d waste heat r e c o v e r y , t h e e x p e n d i t u r e o f e n e r g y in distillation (alcohol r e c o v e r y ) can b e g r e a t l y reduced. Such e n e r g y savings h a v e been indust r i a l l y demonstrated in t h r e e systems described in t h i s paper. F o r high g r a d e i n d u s t r i a l ethanol p r o d u c t i o n , a steam consumption o f 3.0-4.2 K g / l i t e r (25-35 Ib/U.S. gallon) o f looo G.L. alcohol i s realized. F o r motor fuel g r a d e a n h y d r o u s alcohol, t h e steam consumption is 1.8 t o 2.5 K g / l i t e r (15-20 Ib/U.S. gallon) o f 99.5' G.L. alcohol, a n d f o r h y d r o u s motor f u e l g r a d e alcohol, t h e steam consumption i s 1.2 t o 1.4 K g / l i t e r (10-12 Ib/U.S. gallon) of 96O G . L . alcohol. ALCOHOL D I S T I L L A T I O N O v e r t h e p a s t t w o decades, Raphael Katzen Associates International, I n c . has developed a series o f highly e f f i c i e n t alcohol distillation systems f o r r e c o v e r y of various grades o f e t h y l alcohol f r o m s y n t h e t i c and fermentation feedstocks. For each o f these systems, t h e prime goal i s minimization o f e n e r g y consumption. T h e R K A l l d i s t i l l a t i o n system f o r p r o d u c t i o n o f h i g h q u a l i t y s p i r i t s o r i n d u s t r i a l g r a d e alcohol, uses a f o u r t o w e r d i s t i l l a t i o n t r a i n . The p r o d u c t i s f i r s t q u a l i t y n e u t r a l s p i r i t s a t 96O G.L. (192O U.S. p r o o f ) ethanol. When t h e c r u d e ethanol feed i s obtained by t h e s y n t h e t i c process, e.g., d i r e c t h y d r a t i o n of ethylene, o n l y 3 t o w e r s a r e r e q u i r e d . For motor f u e l g r a d e alcohol, where a high q u a l i t y p r o d u c t i s n o t necessary, simpler abbreviated systems a r e used t o r e d u c e investment and o p e r a t i n g costs. PRODUCTION OF 96' G.L. HYDROUS I N D U S T R I A L ALCOHOL

Of

I T h e distillation system i s shown in F i g u r e 1 ( ,2). T h e process has been successfully operated commercially w i t h f o u r d i f f e r e n t fermentation feedstocks, namely, molasses, g r a i n ( c o r n o r milo), c o r n wet m i l l i n g middlings, and s u l f i t e waste l i q u o r . In addition, it has been operated w i t h an ethylene-based s y n t h e t i c c r u d e .

309

Beer from t h e fermenters, c o n t a i n i n g approximately 6-8 w t % alcohol total solids (suspended a n d dissolved) i s preheated t o near a n d %IO% saturation t e m p e r a t u r e a n d f e d t o t h e beer s t i l l . A n overhead condensed p r o d u c t , a t 75-85O G.L. (150'-170 U.S. p r o o f ) i s t a k e n t o t h e high wines drum, and t h e bottoms liquid (stillage), containing n o t more t h a n 0.02 w t % alcohol, is t r e a t e d f u r t h e r f o r animal feed production. The high wines d i s t i l l a t e f r o m t h e beer s t i l l i s mixed w i t h recycled alcohol from t h e c o n c e n t r a t i n g tower a n d t h e combined stream is f e d t o t h e extractive distillation tower. T h e e x t r a c t i v e tower i s designed t o separate s u b s t a n t i a l l y all i m p u r i ties; aldehydes, esters, a n d h i g h e r alcohols f r o m t h e ethanol. T h e e x t r a c t i o n technique relies on t h e v o l a t i l i t y i n v e r s i o n o f t h e h i g h e r alcohols w i t h respect t o ethanol in solutions c o n t a i n i n g high concentrations o f water. T h e n e t r e s u l t i s t h a t a s u b s t a n t i a l l y p u r e ethanol/water m i x t u r e i s r e moved f r o m t h e bottom o f t h e e x t r a c t i v e tower while t h e i m p u r i t i e s are t a k e n overhead. Dilute alcohol f r o m t h e base o f t h e e x t r a c t i v e tower i s s t r i p p e d a n d A heads p u r g e concentrated t o p r o d u c t s t r e n g t h in t h e r e c t i f y i n g tower. i s taken f r o m t h e overhead condensate. P r o d u c t ethanol a t 96O G.L. (192' U . S . proof) is w i t h d r a w n near t h e t o p o f t h e r e c t i f y i n g tower, and a water stream, c o n t a i n i n g t r a c e amounts o f alcohol, is d i s c h a r g e d f r o m t h e base. Heads and side d r a w fusel oil p u r g e s are f e d t o t h e concentrating t o w e r to p r e v e n t a n y buildup of i m p u r i t i e s in t h e r e c t i f y i n g tower. The overhead stream f r o m t h e e x t r a c t i v e t o w e r also i s f e d t o t h e concentrating tower. Heads a n d f u s e l o i l a r e concentrated in t h i s tower and removed f r o m the system, w i t h t h e recovered alcohol b e i n g recycled t o t h e e x t r a c t i v e tower. Steam economy i s achieved by multi-stage p r e h e a t i n g o f beer feed, a n d by o p e r a t i n g t h e e x t r a c t i v e a n d c o n c e n t r a t i n g towers a t h i g h e r press u r e s . T h e overheads f r o m these p r e s s u r e t o w e r s s u p p l y thermal e n e r g y to t h e reboilers o f t h e r e c t i f y i n g t o w e r . Such p r e s s u r e cascading r e s u l t s in a 30 t o 50% r e d u c t i o n in virgin steam.. The k e y f e a t u r e s o f t h e R K A l l high q u a l i t y alcohol d i s t i l l a t i o n system are: 1. E x t r a c t i v e d i s t i l l a t i o n accomplishes a h i g h e r degree of i m p u r i t y Product removal t h a n i s possible in more conventional systems. ethanol contains o n l y 20-30 ppm o f total i m p u r i t i e s . T h e use of p r e s s u r e cascading permits substantial heat r e c o v e r y a n d re-use. In t h e system d e s c r i b e d above and in f i g u r e 1, t h e e x t r a c t i o n tower a n d c o n c e n t r a t i n g tower a r e operated a t a p r e s sure higher than t h e rectifying tower. The overhead vapors

2.

f r o m these p r e s s u r e towers s u p p l y thermal e n e r g y t o t h e r e c t i f y i n g tower reboilers. B y o p e r a t i n g in t h i s manner, t h e steam usage i s k e p t t o a minimum. Commercial facilities u s i n g t h i s p r e s s u r e cascading technique, show steam usages o f o n l y 3.0 t o 4.2 K g o f steam p e r l i t e r (25 t o 35 Ib/gal) o f 96O G.L. (192O U.S. p r o o f ) ethanol compared t o 6.0 K g / l i t e r in e a r l i e r conventional systems.

3. 4.

Substantially all (95 t o 98%) of t h e ethanol in t h e c r u d e feed i s recovered as f i r s t g r a d e p r o d u c t . Design of highly e f f i c i e n t t o w e r t r a y s permits high t u r n d o w n capability. These t r a y s are designed t o b e self-descaling in t h e s t r i p p i n g section o f t h e beer towers. A highly advanced c o n t r o l system, developed t h r o u g h y e a r s o f experience, p r o v i d e s f o r sustained stable operation, w i t h o n l y p a r t - t i m e attention of an operation r e q u i r e d . Product quality i s maintained w i t h less t h a n 30 p a r t s p e r million o f t o t a l i m p u r i t i e s . Permanganate time is in excess o f 60 minutes. G. L . ) ALCOHOL

5.

PRODUCTION OF ANHYDROUS (99.5'-99.98'

A n h y d r o u s alcohol i s p r o d u c e d by azeotropic distillation. A high g r a d e p r o d u c t of 99.98O G . L . (199.96O U.S. p r o o f ) concentration is p r o duced f o r use in food a n d pharmaceutical aerosol preparations. A prod u c t o f 99.5O G . L . (199O U.S. p r o o f ) concentration i s p r o d u c e d f o r b l e n d i n g w i t h gasoline f o r motor f u e l . T h e Katzen two-tower d e h y d r a t i n g system design (see F i g u r e 2) has been installed a n d successfully operated in seven d i f f e r e n t alcohol p l a n t s in N o r t h America a n d t h e C a r r i b e a n . T h e 96' G.L. (192O U.S. p r o o f ) p r o d u c t i s w i t h d r a w n f r o m t h e side o f t h e r e c t i f i e r in t h e h y d r o u s d i s t i l l a t i o n process. T h e h y d r o u s alcohol i s f e d t o an atmospheric d e h y d r a t i n g tower. Removal o f water f r o m t h e feed i s achieved by t h e use o f benzene, heptane, cyclohexane, o r o t h e r suitable e n t r a i n i n g agent. A t e r n a r y azeotrope i s taken overhead f r o m t h e d e h y drating tower. T h e overhead vapors a r e condensed and t h e - t w o liquid phases a r e separated in a decanter. T h e e n t r a i n e r - r i c h phase is r e f l u x e d t o t h e d e h y d r a t i n g t o w e r . A reboiler is used t o s u p p l y v a p o r t o t h i s t o w e r w i t h heat supplied by e i t h e r low p r e s s u r e steam, recovered f l a s h v a p o r , o r h o t e f f l u e n t a n d condensate streams f r o m t h e h y d r o u s alcohol unit.

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T h e aqueous phase f r o m t h e decanter i s f e d t o a s t r i p p e r . The e n t r a i n i n g agent i s recovered, along w i t h alcohol, in t h e overhead v a p o r . Water is removed f r o m t h e bottom of t h e s t r i p p e r . D i r e c t steam may b e used in t h i s s t r i p p e r . The bottoms stream f r o m t h e azeotropic d e h y d r a t i n g tower a n h y d r o u s alcohol p r o d u c t . is the

Design know-how consists of optimizing t h e balance between capital costs and u t i l i t y consumption, w i t h stable c o n t r o l . Specific features which c o n t r i b u t e t o o v e r a l l process e f f i c i e n c y a n d r e l i a b i l i t y o t t h e R K A l l a n h y d r o u s alcohol d i s t i l l a t i o n system are:

1.
2.

Use o f a common condenser a n d decanter f o r t h e d e h y d r a t i o n a n d stripping towers t o reduce capital costs. Design o f h i g h l y e f f i c i e n t tower t r a y s f o r high t u r n d o w n capability. Low consumption o f e n t r a i n i n g a g e n t (less t h a n 0.1 K g p e r 1,000 l i t e r s o f a n h y d r o u s alcohoi). Low consumption o f steam (1 t o 1.5 K g / l i t e r o r 8.3 to 12.5 Ib/gallon of a n h y d r o u s alcohol), o r equivalent h o t condensate o r waste streams.

3. 4.
.

PRODUCTION OF ANHYDROUS MOTOR FUEL GRADE ALCOHOL For motor f u e l g r a d e alcohol, t h e beer feed is preheated in a m u l t i stage heat exchange sequence. A p r e s s u r e s t r i p p e r - r e c t i f i e r (see F i g u r e 3) i s used t o separate t h e beer feed i n t o a n overhead f r a c t i o n o f about 95' G.L. (190' U.S. p r o o f ) alcohol and a bottoms stream containing less t h a n 0.02 w t % alcohol. Side draws are made t o remove fusel oils. These oils a r e recovered by water washing, and reblended as a component o f t h e motor fuel g r a d e alcohol. I n addition, a p a s t e u r i z i n g section is used t o concentrate low b o i l i n g i m p u r i t i e s . These a r e removed by t a k i n g a small heads d r a w w h i c h is b u r n e d in t h e p i a n t r e b o i l e r . Dehydration of the Energy is h y d r o u s p r o d u c t i s accomplished in t w o additional towers. supplied t o t h e r e b o i l e r s o f t h e t w o towers in t h e d e h y d r a t i o n step by condensing t h e overhead vapors f r o m t h e p r e s s u r e s t r i p p e r - r e c t i f i e r . By o p e r a t i n g t h e b e e r s t r i p p e r - r e c t i f i e r a t a h i g h e r p r e s s u r e (3) t h a n t h e two-tower d e h y d r a t i o n system, v e r y low t o t a l steam consumption can b e achieved. T h e steam usage i s 1 . 8 t o 2.4 K g / l i t e r (15 t o 20 Ib/gallon) of 9 9 S 0 G . L . (199' U.S. p r o o f ) motor f u e l g r a d e alcohol p r o d u c t (5).

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I
I

PRODUCTION OF HYDROUS MOTOR FUEL GRADE ALCOHOL For a p r o d u c t t o b e u t i l i z e d in NEAT alcohol engines (no gasoline in t h e blend), f u r t h e r steam economy can be achieved when o n l y 85-95' G.L. (170'-190' U.S. p r o o f ) alcohol p r o d u c t i s desired. T h i s i s accomplished by s p l i t t i n g t h e s t r i p p i n g - r e c t i f y i n g d u t i e s between two towers (see F i g u r e 4, Ref. T h e f i r s t s t r i p p e r - r e c t i f i e r tower is operated a t a p r e s s u r e h i g h e r than t h e second tower a n d receives 50 t o 60% o f t h e beer feed. T h e overhead v a p o r s f r o m t h e f i r s t tower a r e used t o boil up v a p o r i n t h e second tower.

4. )

T h e steam usage i s 1.2 t o 1.5 K g / l i t e r ( I O t o 12 Ib/gallon) o f 85'-96' G.L. (170-1920 U.S. p r o o f ) motor f u e l g r a d e alcohol (on a 100% ethanol Along w i t h steam economy, cooling water requirements a r e reduced basis). proportionately. SUMMARY A summary o f investment f o r t y p i c a l low e n e r g y d i s t i l l a t i o n systems (shown in -Figures 1 t h r o u g h 4) f o r p r o d u c t i o n o f 190 MM l i t e r / y e a r (50 MM USGPY) alcohols i s g i v e n in Table 1 . Also, shown are t h e steam, cooling water and electric e n e r g y requirements f o r each system. REFERENCES

1. 2.

U.S. Patent 3,445,345, E x t r a c t i v e Distillation o f C - I t o C - 3 Alcohols a n d Subsequent Distillation o f P u r g e Streams, May 20, 1969.
U . S . Patent 3,990,952, November 9, 1976.

Improvement in Alcohol Distillation

Process,

3.

U.S. Patent Application No. 958,533, Distillation Method a n d A p p a r atus f o r Making Motor Fuel Grade A n h y d r o u s Alcohol, November 7, 1978. U .S. Patent Application, Novel E n e r g y E f f i c i e n t Process f o r Product i o n of 170 t o 190' Proof Alcohol. Raphael Katzen Associates, Grain Motor Fuel Alcohol, Economic Assessment S t u d y , U .S. DOE C o n t r a c t No. June, 1979. Technical and EJ-78-C-6639,

4.

5.

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TABLE 1

LOW ENERGY D I S T I L L A T ION SYSTEMS SUMMARY OF I N V E S T M E N T A N D U T I L I T I E S

190 MM l i t e r s / y r (50 MM g a l l o n s / y r )
High Grade (96' G . L . ) Industrial Alcohol Figure Alcohol P r o d u c t , U.S. Proof Anhydrous Anhydrous

(looo G . L . )
Industrial A Ico h o l

(99.5O G . L . )
Motor Fuel Alcohol

Hydrous Motor Fuel Grade A Icoho1

2 200

3 199

4 190

190

Dis t iII a t i o n U nit

Investment $MM U . S . Steam U s a g e Kg/liter (Ib/gallon) Cooling Water MT/hr Electric Power kw

7.3 4.1 (34) 1866 289

2.8 1.4 (11.7) 934 31

6.1 2.2 (18) 1311 133

3.4 1.2 (10) 182 177

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