Review of Western European and Japanese Iron and Steel ...infohouse.p2ric.org/ref/15/14233.pdf ·...

United- States Environmental Agency

31’. Cd--. t ? c f k ,

Industrial Environmental Research EPA-600/2-79-002 Protection La bora torv Januarv 1979

Research Triangle Park NC 2771 1

Research and Development

Review of Western European and Iron and Steel

Japanese Industry

Exemplary Water Pollution Control Technology

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Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into nine series. These nine broad cate- gories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The nine series are:

1. Environmental Health Effects Research

2. Environmental Protection Technology

3. Ecological Research

4. Environmental Monitoring

5. Socioeconomic Environmental Studies

6. Scientific and Technical Assessment Reports (STAR)

7 . Interagency Energy-Environment Research and Development

8. "Special" Reports

9. Miscellaneous Reports

This report has been assigned to the ENVIRONMENTAL PROTECTION TECH- NOLOGY series. This series describes research performed to develop and demonstrate instrumentation, equipment, and methodology to repair or prevent environmental degradation from point and non-point sources of pollution. This work provides the new or improved technology required for the control and treatment of pollution sources to meet environmental quality standards.

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This report has been reviewed by the U.S. Environmental Protection Agency, and approved for publication. Approval does not signify that the contents necessarily reflect the views and policy of the Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use.

This document is available to the public through the National Technical Informa- tion Service, Springfield, Virginia 22161.

?

E PA-60012-79-002

January 1979

Review of Western European and Japanese Iron and Steel Industry

Exemplary Water Pollution Control Technology

H.M. Tockmam, G. Swaminathan, and J.D. Stockham

IIT Research Institute 10 West 35th Street

Chicago, Illinois 6061 6

Contract No. 68-02-261 7 Task No. 2-3

Program Element No. 1BB610

EPA Project Officer: John S. Ruppersberger

Industrial Environmental Research Laboratory Office of Energy, Minerals, and Industry

Research Triangle Park, NC 2771 1

Prepared for

US. ENVIRONMENTAL PROTECTION AGENCY Office of Research and Development

. Washington, DC 20460

DISCLAIMER

Th is r e p o r t has been rev iewed by t h e I n d u s t r i a l Environmental Research Labora tory , U.S. Env i ronmenta l P r o t e c t i o n Agency, and approved f o r p u b l i c a t i o n . Approval does n o t s i g n i f y t h a t t h e con ten ts n e c e s s a r i l y r e f l e c t t h e v iews and p o l i c i e s o f t h e U.S. Envi ronmenta l P r o t e c t i o n Agency, no r does ment ion o f t r a d e names o r commercial p roduc ts c o n s t i t u t e endorsement o r recommendation f o r use.

i

ABS TRA C T Current Western European and Japanese water pol 1 ut ion control technology

i n the i ron and s t e e l industry was i d e n t i f i e d by means of a l i t e r a t u r e survey and telephone and T E L E X communications, We found t h a t t h e Japanese favor re - cycle technology whereas British and Western European s t e e l p lan ts p rac t i ce a va r i ab le recyc le r a t e . Summaries o f typical po l lu t ion control operat ions a r e described and comparative data a r e provided,

i i

CONTENTS

A b s t r a c t . . ........................................................

i v F igu res

Ta b l es

Acknowledgement

V

v i

1. I n t r o d u c t i o n

2,

3, Recommendations

4. The Japanese S t e e l I n d u s t r y

5. The Western European S tee l I n d u s t r y

Concl u s i o n s

Appendix A

Appendix B

5

6

1 7

2 6

2 8

iil’

FIGURES

Number Page

1 Japanese Investment in Pollution Control Equipment , . . , . . 7

2 . Flow Chart o f the Dry Coke Quenching Process . . . . . . 11

3. Flow C h a r t of the Nippon Steel Corp. Ion Exchange Process. . a 1 3

4 . Flow Char t of Process: Coke Oven Liquor Treatment . e , , * 1 5

5. Flow Char t o f the Chemical Treatment of Effluent Used in Appleby-Frodingham Works. . , . . . . . . , . . . . . . . 2 2

iv

TABLES

Number Page

1, Comparison o f Techniques . . . . . . . . . . . . . . . . . . - 4

2. Comparative Operating Data From a Japanese Integrated Iron and Steel Plant . . . . . . . . . . . . . . . . . . . . 9

3. Dis t r ibu t ion o f Water Intake a t B r i t i s h Steel Corporat ion 's Appleby-Frodingham Works . . . . . . . . . . . . . . . . . . I8

4. Approximate Composition o f Spent Ammoniacal Liquor . . . . 2 1 9

5. Blast Furnace Gas Cleaning Systems - Maximum Concentration . . . . . of Toxic Const i tuents i n Treated Eff luent Water. - 2 0

6. Analysis of Recirculat ing Water i n Blas t Furnace Gas Cleaning . . . . . . . . . . . . . . . System a t Appleby-Frodingham - 2 1

7 . Permissible Impuri t ies i n Indus t r ia l Wastewater i n West Germany. . . . . . . . . . . . . . . . . . . . . . . . . . ' 2 4

Y

ACKNOWLEDGMENTS

We g r a t e f u l l y acknowledge the following for t h e i r a s s i s t ance and cooperation i n support o f th i s p ro jec t : Dr. K . S . Goto, Tokyo I n s t i t u t e of Technology, Dr. R . L . Cooper, Brit ish Carbonization Research Association, Dr. B . J . Borne, Water Pol lut ion Research Laboratory, Stevenage, Kerts , U.K., Dr. Dennis F i n n , I IT Research I n s t i t u t e , Chicago, IL, and Dr. George S t . P i e r r e , Professor of Metallurgy, Ohio S t a t e Universi ty , Columbus, O H .

v i

SECTION 1

I NTRODUCTI ON

I n 1971, t h e I n t e r n a t i o n a l I r o n and S t e e l I n s t i t u t e s e t up a Committee on Environmental M a t t e r s t o demonstrate i t s a c t i v e suppor t o f measures t o conserve and improve t h e q u a l i t y o f w o r l d env i ronmenta l c o n d i t i o n s , I t d i d n o t a t tempt t o m in im ize t h e c o m p l e x i t y of t h e o v e r a l l problems faced by t h e s t e e l i n d u s t r y . The i n s t i t u t e d i d b e l i e v e , however, t h a t accep tab le s o l u t i o n s c o u l d be achieved by an exchange o f i n f o r m a t i o n among i n d u s t r i e s on a w o r l d - wide bas i s , as w e l l as by v o l u n t a r y c o o p e r a t i o n w i t h l o c a l c o n t r o l and con- s e r v a t i o n o r g a n i z a t i o n s ,

A t p resen t , s i g n i f i c a n t problems remain t o be so lved. I n response t o t h i s , t h e i r o n and s t e e l i n d u s t r i e s o f t h e U n i t e d S t a t e s , Japan and West Germany have been s t e a d i l y i n c r e a s i n g investments i n p o l l u t i o n c o n t r o l , I n t h e U n i t e d S ta tes , t h e s t e e l i n d u s t r y ranks among t h e l e a d i n g manufacturers i n c a p i t a l expend i tu res f o r p o l l u t i o n c o n t r o l . H i l l ’ , shows th ’a t between 1971 and 1972, t h e U n i t e d S t a t e s s t e e l i n d u s t r y spent $400 m i l l i o n on a i r and water p o l l u t i o n c o n t r o l - about 8 pe rcen t o f t h e t o t a l spent t y a l l manu fac tu r ing i n d u s t r i e s . I n 1973, t h e s t e e l i n d u s t r y ’ s p o l l u t i o n c o n t r o l e x p e n d i t u r e was $276 m i l l i o n o r 13.6 percen t o f t h e t o t a l expend i tu res o f t h e s t e e l i n d u s t r y . ex t ima ted $517 m i l l i o n spent on p o l l u t i o n c o n t r o l o r an es t ima ted 18.8 pe rcen t o f t o t a l expend i tu res .

A survey conducted by McGraw-

By 1976, t h a t f i g u r e i nc reased t o an

The f i g u r e s a v a i l a b l e f o r Germany and Japan a l s o i n d i c a t e a s teady growth i n p o l l u t i o n c o n t r o l investment . Between 1970 and 1974, t h e German inves tmen t grew from.7.3 t o 12 percen t o f t h e t o t a l c a p i t a l i nves tmen t . S i m i l a r l y , t h e Japanese i n d u s t r y i nc reased i t s i nves tmen t f rom 4 t o 20 pe rcen t i n a m a t t e r o f 10 yea rs .

The U.S. i r o n and s t e e l i n d u s t r y t h u s compares v e r y f a v o r a b l y w i t h f o r e i g n p l a n t s . a r e r e l a t i v e l y new, which makes i t e a s i e r t o implement t h e use o f newer equipment and techniques.

Most o f t h e Japanese and Western European p l a n t s , however,

The o b j e c t i v e o f t h i s s tudy was t o survey f o r e i g n techniques i n water p o l l u t i o n c o n t r o l and t o i d e n t i f y any advances which m igh t be s t u d i e d f o r t r a n s f e r t o t h e Unived S t a t e s i r o n and s t e e l i n d u s t r y . S ince t h e l i m i t e d f r e s h water supp ly i n Japan and areas o f Western Europe n e c e s s i t a t e a h i g h degree o f wate r r e c y c l e , t h i s survey focused on water p o l l u t i o n c o n t r o l techniques o f i r o n and s t e e l p l a n t s p r a c t i c i n g e i t h e r a h i g h degree o f water

‘ I r o n and S tee l I n t e r n a t i o n a l , June, 1974, pp. 228-237

1

r e c y c l e o r exemplary p o l l u t i o n abatement c a p a b i l i t y ,

I n t h e r e p o r t , t h e Japanese i r o n and s t e e l p l a n t s a r e cons ide red as one group, and t h e Western European p l a n t s as ano the r one. The g u i d e l i n e s s e t by t h e d i f f e r e n t c o u n t r i e s have been ob ta ined , and t h e a c t u a l performance o f t h e exemplary p l a n t s a r e compared w i t h these g u i d e l i n e s wherever p o s s i b l e , T h i s r e p o r t a l s o i n c l u d e s conc lus ions and recommendations wh ich a r e concerned w i t h t h e a p p l i c a b i l i t y o f some o f t hese exemplary techn iques , Some recom- mendat ions have been made sugges t ing improvements i n methodology f o r c o l - l e c t i n g i n f o r m a t i o n on a p r o j e c t o f t h i s n a t u r e ,

2

SECTION 2

CONCLUSIONS

I n genera l , Japanese and B r i t i s h s t e e l p l a n t s use more s a l i n e water t h a n t h e i r U.S. c o u n t e r p a r t s , who u s u a l l y r e l y on f r e s h wa te r sources, From t h e a v a i l a b l e da ta , Bethlehem S t e e l ' s Sparrows P o i n t i s t h e o n l y American p l a n t u s i n g seawater. American p l a n t s r e c y c l e f rom 1 5 t o 80 pe rcen t o f t h e f resh wa te r . Japanese p l a n t s , however, r e c y c l e about 90 p e r c e n t o f t h e f resh water used.

S ince f r e s h wa te r i s cheap and r e a d i l y a v a i l a b l e i n t h e U . S . ,

The B r i t i s h s t e e l p l a n t s a l s o have a h i g h degree o f f r e s h wa te r r e c y c l i n g , 2 t o 90 pe rcen t o f t h e wa te r used from a l l sources. r e c y c l e a r e p r a c t i c e d i n t h e i n l a n d p l a n t s , whereas t h e s m a l l e r f i g u r e s a r e f o r c o a s t a l p l a n t s u s i n g sea water . P l a n t s u s i n g s a l i n e water r e c y c l e o n l y t h e i r f r e s h water . European p l a n t s a r e s i m i l a r t o those o f American p l a n t s . For example, t h e B r i t i s h C a r b o n i z a t i o n Research A s s o c i a t i o n has been conduc t ing r e s e a r c h on t h e b i o l o g i c a l - o x i d a t i o n process f o r e f f l u e n t c o n t r o l

The Japanese i n d u s t r y uses some r e l a t i v e l y modern techniques, examples o f which a r e :

(1) d r y coke quenching, ( 2 )

H ighe r degrees o f

The techniques used by t h e B r i t i s h and o t h e r Western

i o n exchange r e s i n method f o r p i c k l i n g r i n s e waste water t r e a t m e n t .

Based on d i s c u s s i o n s w i t h o u r in-house exper t s , we conclude t h a t : (1) U.S. i r o n and s t e e l p l a n t s do n o t p r a c t i c e water r e c y c l i n g t o as

h i g h a degree as t h e f o r e i g n p l a n t s , p r i m a r i l y due t o t h e a v a i l - a b i l i t y of cheap and p l e n t i f u l f r e s h water i n t h e U,S,

( 2 ) Japanese p l a n t s use modern techn iques because t h e i r p l a n t s a r e newer. U.S. p l a n t s c o u l d a l s o implement these techniques, g i v e n s u f f i c i e n t i n c e n t i v e and space.

(More Table 1 i s p rov ided f o r comparison o f U.S, and f o r e i g n p l a n t s , i n f o r m a t i o n i s c l e a r l y needed f rom Western European p l a n t s . ) t h e d r y coke quenching (DCQ) and t h e i o n exchange processes a r e exemplary techniques used by t h e Japanese i n d u s t r y . on p o l l u t i o n c o n t r o l investments, t h e U.S. i r o n and s t e e l p l a n t s r a t e f a v o r a b l y w i t h f o r e i g n p l a n t s .

As can be seen,

As can be seen by comparing da ta

I t i s n o t f e a s i b l e i n t h i s survey t o pe r fo rm an economic a n a l y s i s o f t h e a p p l i c a b i l i t y o f t r a n s f e r r i n g f o r e i g n techn iques . s p e c i f i c da ta i t would be necessary t o do an i n - d e p t h s tudy on a case by case b a s i s . T h i s t y p e o f a n a l y s i s was beyond t h e scope o f t h i s survey r e p o r t ,

I n o r d e r t o generate

3

TABLE 1

COMPARISON OF TECHNIQUES

1. Use o f seawater Used a t Bethlehem * J N , A , ** N . A . S tee l '.s Sparrows P o i n t P l a n t

2. Degree o f f reshwa te r A v e r y wide range, around around N.A. N . A . r e c y c l e depending on t h e 90% 90%

age o f t h e p l a n t and l o c a t i o n

3. Phys i ca l t rea tmen t J ( s e t t l i n g , f i l t r a t i o n , e t c . )

J J J J

4. U l t r a h i g h Rate f i l t r a t i o n J J N.A. N.A. N.A.

5. Dry Coke Quenching Not i n use J process

6. I o n Exchange Process f o r Not i n use J t h e P i c k l e L i q u o r Wastes

7 . B i o l o g i c a l O x i d a t i o n J Process

8. Pol 1 u t i o n Con t ro l ,18.8% Inves tment ( % o f C a p i t a l Inves tment )

Not i n use N.A. N.A.

N . A . I n t h e be- N.A. g i n n i n g s tages

J J J J

16-20% N.A . 512% *** N , A .

* J Technique c u r r e n t l y i n use **N.A. I n f o r m a t i o n n o t a v a i l a b l e

Es t i ma t e ***

SECTION 3

RECOMMENDATIONS

Further research in to foreign iron a n d s t ee l pol lut ion control should In order t o evaluate the f e a s T b i l i t y o f technology t r a n s f e r

There i s a l so more information a v a i l a b l e than this survey covered,

be conducted. and to v e r i f y the spec i f i c operattonal s ta te -of - the-ar t i n Europe a n d Japan, more in-depth, operational information on a wide range of s t ee l p lan ts i s required. For example, new guidel ines a r e c u r r e n t l y being formulated by government and indus t r ia l committees. This information, combined w i t h spec i f i c s obtained t h r o u g h s i t e vi .si ts , should r e s u l t i n a more accurate predict ion o f the u t i l i t y o f technology t r a n s f e r o f foreign water recycle a n d pol lut ion con- t r o l techniques.

A general study of s t ee l plant parameters cor re la ted w i t h e f f luen t l eve l s would answer some a p p l i c a b i l i t y questions. Ranges of plant s i z e , age, output , a n d water source c h a r a c t e r i s t i c s could be matched t o ranges of pol lut ion capab i l i t y , yielding data helpful i n technology t r a n s f e r ana lys i s I t must be noted t h a t recycle and pol lut ion control systems a r e designed on a case by case bas i s . T h u s , before a new pol lut ion control system can be recommended, a case by case ana lys i s of t he above var iab les should be performed.

We would a l so suggest t h a t d i s tance and language ba r r i e r s could be eliminated by o n - s i t e a c t i v i t y . ceiving information would t h u s be minimized. a l l e v i a t e some of the hes i ta t ion of s t ee l companies t o discuss t h e i r pol- l u t ion control data ' . An intergovernmental agreement o r project m i g h t a l s o f a c i l i t a t e access t o these p lan ts .

Delays i n t r a n s l a t i n g questions and r e - On-site interviews m i g h t a l so

Another area of research would be in-depth s tudies of individual exemplary p lan ts . Exemplary plants w i t h t he newest, model equipment can be e i t h e r those recent ly constructed, such as Nippon Kokan Corporation's Ogishima plant o r o lder plants w i t h recent pol lut ion control r e t r o f i t .

5

SECTION 4

THE JAPANESE STEEL INDUSTRY

The Japanese i r o n and s t e e l i n d u s t r y i s one o f t h e more s o p h i s t i c a t e d i n t h e wor ld . d u r i n g t h e l a s t decade. c o n t r o l i n Japan have become p r o g r e s s i v e l y s t r i c t e r . The Japanese i n d u s t r y c u r r e n t l y spends 1 6 t o 20 percen t o f i t s c a p i t a l investment on p o l l u t i o n c o n t r o l 2 . As can be seen f rom F i g u r e 1, t h e p r o p o r t i o n o f p o l l u t i o n c o n t r o l investment has i nc reased from 4 t o 20 percen t i n a span o f 10 y e a r s 3 . T h i s 20 percen t compares w i t h a 18.8 percen t f o r t h e U n i t e d S t a t e s and about 12 percen t f o r West Germany.

The Japanese have b u i l t many modern s tee lmak ing f a c i l i t i e s W i t h e v e r y yea r , r e g u l a t i o n s f o r env i ronmenta l

Acco rd ing t o M r . Minora Mizuno (General Manager, Environmental C o n t r o l

( a )

( b )

Department, Nippon Kokan C o r p o r a t i o n ) , t h e f o l l o w i n g a r e r e c e n t developments i n water p o l l u t i o n c o n t r o l i n Japan4:

Over 90 p e r c e n t o f t h e water used a t t h e Japanese S t e e l Works i s r e t o v e r e d . Coke Oven Gas Coo l i ng H20 i s t r e a t e d by t h e a c t i v a t e d Sludge Process, Aerobic b a c t e r i a remove t h e ammonia and phenol .

OPERATING DATA FOR A JAPANESE I R O N AND STEEL PLANT

We s h a l l examine more c l o s e l y t h e o p e r a t i o n s t a t i s t i c s o f an exemplary Japanese i r o n and s t e e l p lan t ' , which has i n v e s t e d about 20 p e r c e n t o f i t s c a p i t a l i n p o l l u t i o n c o n t r o l equipment. a c a p a c i t y o f 4.3 x l o 6 Kg o f p i g i r o n per day and two b a s i c oxygen furnaces t h a t each p r o c e s s ' 0 - 2 5 x l o 6 Kg. o f s t e e l each. f o r t h e p l a n t ' s e l e c t r i c power s t a t i o n . t h e r e i s no f u r t h e r con tamina t ion except thg rma l . t o t h e sea w i t h a maximum temperature of 38 C . t o meet d u r i n g t h e summer. l e v e l s o r c o r r o s i o n i n h i b i t i n g techniques used by t h e i n d u s t r y , shou ld be t r e a t e d b e f o r e use as a c o o l a n t , n iques a r e :

The p l a n t has one b l a s t f u rnace w i t h

When t h e water l e a v e s t h e system, Seawater i s used as a c o o l a n t

T h i s water must be r e t u r n e d T h i s i s a d i f f i c u l t s tandard

No i n f o r m a t i o n has been p r o v i d e d on c o r r o s i o n T h i s seawater

Some o f t h e commonly used tech -

2Chemical and Eng ineer ing News, J u l y 28, 1975, pp. 10-11. Transac t i ons of t h e I r o n and S tee l I n s t i t u t e o f Japan, F i g u r e 12, V o l . 17, No, 8, 1977, pp, 441. Stee l Times, May, 1973, pp. 388,

'Unpublished i n f o r m a t i o n p rov ided by D r . K.S. Goto, Tokyo I n s t i t u t e o f Tech.

3

4

6

Figure 1. Investment i n Japans s t e e l industry f o r pol 1 ution control equipment.

Trans Iron & Steel I n s t i t u t e o f Japan,Vol 17,No 8,1977,~441 Reprinted w i t h permission

7

1. I o n Exchange 2, E l e c t r o d i a l y s i s 3. Reverse Osmosis

The d a i l y i n t a k e o f process water i s 1 - 3 x l o 9 Kg. o f which 1.27 x l o 9 Kg. o r 97.8 pe rcen t i s r e c y c l e d . d a i l y b a s i s i n t h i s p l a n t .

30 x l o 6 Kg, (2.2 p e r c e n t ) i s consumed on a

The p l a n t has f o u r water s to rage poo ls and n i n e u n i t s of wastewater t rea tmen t systems, o f which two use t h e a c t i v a t e d s ludge process w i t h a c t i - va ted carbon.

Table 2 compares t h e o p e r a t i n g c h a r a c t e r i s t i c s o f t h i s p l a n t w i t h Japanese r e g u l a t i o n va lues. b e t t e r t han t h e r e g u l a t i o n v a l u e . t h e Japanese e f f l u e n t g u i d e l i n e s ,

As can be seen, o p e r a t i n g va lues a r e u n i f o r m l y The r e g u l a t i o n va lues g i v e us an i d e a o f

The da ta i n Table 2 were o b t a i n e d w i t h c o n s i d e r a b l e e f f o r t as Japanese s t e e l p l a n t s a r e v e r y s e c r e t i v e about t h e i r o p e r a t i n g va lues , f e e l i n g t h a t f u r t h e r e f f o r t s should be made t o o b t a i n t h e o p e r a t i n g d a t a o f a l l exemplary p l a n t s , as w e l l as t h e t r a n s f e r o f t echno logy f rom t h i s p l a n t t o t h e U n i t e d S t a t e s .

I t i s o u r

Some o f t h e p o l l u t i o n c o n t r o l e f f o r t s o f Nippon Kokan Corpo ra t i on (NKK) and Nippon S t e e l C o r p o r a t i o n (NSC) were exemplary, desc r ibed as w e l l as seve ra l s p e c i f i c techniques used by NKK and NSC.

NKK's e f f o r t s a r e b r i e f l y

THE N I PPON KOKAN CORPORATION (NKK)

NKK, t h e second l a r g e s t s t e e l c o r p o r a t i o n i n Japan, spent about $163 m i l l i o n f o r p o l l u t i o n c o n t r o l between 1971 and 19746. t h a t s tee lmak ing p o l l u t i o n c o s t s a r e about $6.00 per 1000 Kg. i n g o t . NKK's Ogishima p r o j e c t , scheduled f o r comp le t i on by t h e end o f 1978, has been he ra lded as t h e most modern p l a n t i n t h e w o r l d 7 . I t s o p e r a t i n g va lues a r e s i m i l a r t o those shown i n Table 2. The K e i h i n works i s c u r r e n t l y be ing phased o u t and i s b e i n g r e p l a c e d by t h e Ogishima p l a n t . a l r e a d y o p e r a t i o n a l .

I t i s now c a l c u l a t e d

The f i r s t phase i s

The Fuluyama and K e i h i n Works

The water t r e a t m e n t equipment a t Fukuyama i n c o r p o r a t e s des ign techno logy

0

0

ob ta ined f rom t h e U n i t e d S t a t e s : The cascade method o f r e c i r c u l a t i o n , which separates t h e water a c c o r d i n g t o i t s q u a l i t y . U l t r a - h i g h - r a t e f i l t r a t i o n f o r t r e a t i n g d i r e c t contact . water a t h o t and c o l d s t r i p m i l l s .

The p l a n t s a t Fukuyama and K e i h i n have v e r y h i g h water r e c i r c u l a t i o n

I r o n and S t e e l I n t e r n a t i o n a l , June 1974, pp, 205-227. 6

71ron and S tee l I n t e r n a t i o n a l , Vol . 50, No. 2, A p r i l , 1977, pp. 75.

8

TABLE 2

COMPOSITIONS OF WATER AFTER TREATMENT

(Average Values o f Opera t i on Data Over a P e r i o d o f 4 Months)

ROLLING MILL WATER CONSTITUENT BOF DUST CATCHER SPRAYWATER OF COKE OVEN WATER WATER CONTINUOUS CASTING (ACTIVATED SLUDGE)

SLABS

A B A B A B A B

PH 8.0- 8 .3 5.8- 8.6 8.2- 8,: 5.8- 8 . 6 6,6- 7 , l 5,8- 8 ,6 7,6- 7.7 5.8- 8,6

COD (mg / l ) 4 <20 4 - 5 <20 9 -31 30 4 <20

TS S 1 4 -15 <30 <5 <30 5 -12 30 5 - 8 <30 co

O i l s (mg / l ) < 3 < 3 <3 <3 <3 < 3 <3 < 3

-- -- <O e 02 -- S o l u b l e I r o n (mg/ l ) 0.70 3 <o. 02 3

A = a c t u a l values,: B = r e g u l a t i o n va lues; - - - - da ta n o t a v a i l a b l e

P r i v a t e communication f rom D r . Goto

r a t e s : 88 pe rcen t a t t h e K e i h i n and 93 p e r c e n t a t t h e Fukuyama Works. o f t h e water f o r c l e a n i n g b l a s t f u rnace gas i s c i r c u l a t e d th rough a t h i c k e n e r t o t r a p suspended s o l i d s and i s t hen reused. t h e b l a s t f u rnace s l a g . P o l l u t a n t s i n coke oven waste ammonia l i q u o r such as phenol and cyanides a r e removed by an a c t i v a t e d s ludge process. A t Fukuyama, a 2400 m3/day t r e a t m e n t p l a n t was i n s t a l l e d a t t h e c o s t o f about $3 m i l l i o n . I n o r d e r t o e l i m i n a t e any c o l o r a t i o n which m i g h t be p resen t , NKK u t i l i z e s a t rea tmen t p l a n t , wherein c o a g u l a t i o n , sed imen ta t i on , and f i l t r a t i o n a c t i v i t i e s t a k e p lace .

P a r t

Another p a r t i s used f o r c o o l i n g

Water d i scha rged i n t h e c o l d s t r i p m i l l i s t r e a t e d by d i s s o l v e d a i r f l o t a t i o n w i t h c o a g u l a t i n g agents. d ischarged a f t e r r e d u c t i o n , n e u t r a l i z a t i o n , and sed imen ta t i on ,

Water f rom s u r f a c e t r e a t i n g processes i s

Water c o n t a i n i n g h i g h c o n c e n t r a t i o n s o f h y d r o c h l o r i c a c i d i s f i r s t t r e a t e d t o r e c o v e r t h e a c i d and t h e n reused. d r y i n g p l a n t i s ma in ta ined a t t h e K e i h i n Works, where s ludge i s n e u t r a l i z e d , dehydrated, and t h e n d r i e d i n a r o t a r y k i l n f o r r e c o v e r i n g i r o n m a t e r i a l s .

A 60 x l o 3 Kg/day c a p a c i t y

A t t h e K e i h i n Works, a $1.0 m i l l i o n i n c i n e r a t i o n p l a n t processes o i l y s ludge and waste a t a r a t e o f about 800 x l o 3 Kg/month. The o i l separated from t h e waste i s used f o r f u e l . i n c i n e r a t i o n p l a n t processes o i l y wastes and o t h e r r e f u s e a t a c a p a c i t y o f 4.2 x l o 6 Kg/month.

A t t h e Fukuyama Works, a $1.5 m i l l i o n

S P E C I F I C PROCESSES USED BY THE JAPANESE I R O N AND STEEL INDUSTRY

The Japanese s t e e l i n d u s t r y u t i l i z e s some new and exemplary techniques f o r c o n t r o l l i n g i t s water p o l l u t i o n , such as d r y coke quenching and i o n exchange t r e a t m e n t o f p i c k l e l i q u o r water .

Dry Coke Quenching (DCQ)

s c i e n t i s t s and p e r f e c t e d by t h e Japanese ( i n i t i a l l y by t h e Nippon S t e e l C o r p o r a t i o n ) .

The d r y coke quenching process i s a novel t echn ique dev i sed by Russian

I t .has n o t y e t been implemented i n any American p l a n t ,

The process has t h e f o l l o w i n g advantages: 0 0 i t e l i m i n a t e s t h e use o f wa te r e i t saves energy. e i t reduces p o l l u t i o n . 0

i t i s a c l o s e d system.

i t y i e l d s a b e t t e r q u a l i t y coke (no i m p u r i t i e s and a b e t t e r c r y s t a l 1 i n e s t r u c t u r e ) .

I n DCQ, h o t coke pushed o u t f rom t h e ovens i s quenched w i t h r e c i r c u l a t i n g i n e r t gas i n s t e a d o f wa te r . process. dumped i n t o i t s pre-chamber. t h e c o o l i n g chamber, where i n e r t gas absorbs heat f rom t h e coke, coke i s t h e n d ischarged f rom t h e bottom o f t h e quenching chamber.

F i g u r e 2 r e p r e s e n t s t h e f l o w c h a r t f o r t h e DCQ

I t g r a d u a l l y descends f rom t h e pre-chamber t o The coo led The gas,

Red h o t coke i s c a r r i e d t o t h e t o p o f a quenching chamber and

10

i”

1

H LL

11

heated t o temperatures o f about 8OO0C, i s l e d t o a waste hea t b o i l e r , a f t e r i t s d u s t has been removed, t o produce t h e stream f o r heat recove ry . * cooled gas i s s e n t back t o t h e c o o l i n g chamber f o r c i r c u l a t i o n , has 5 DCQ u n i t s , each w i t h a quenching c a p a c i t y of about 70 x lo3 Kg/hr.

The NKK c u r r e n t l y

I o n Exchange Resin Method f o r P i c k l i n g Rinse Water Treatment

The p i c k l i n g process i s a v e r y i m p o r t a n t s t e p i n an i n t e g r a t e d s t e e l p l a n t . Some 50 percen t o f t h e p roduc ts produced i n an i n t e g r a t e d s t e e l works undergoes a c i d p i c k l i n g . ' Water i s used b o t h f o r d i l u t i n g t h e s u l f u r i c o r h y d r o c h l o r i c a c i d i n t h e a c i d b a t h and f o r washing t o s t e e l i n t h e r i n s e tank . T h i s accounts f o r a l a r g e q u a n t i t y of water which should be t r e a t e d .

The usual method f o r t r e a t i n g t h i s wastewater i s by n e u t r a l i z a t i o n and s e t t l i n g . q u i r i n g c o s t l y d i s p o s a l and t rea tmen t . NSC, i n j o i n t research w i t h M i t - s u b i s h i Chemical I n d u s t r i e s L i m i t e d , has developed a new process which employs d i r e c t i o n exchange f o r t h e e f f e c t i v e t rea tmen t o f r i n s e wastewater generated by a c i d p i c k l i n g . Whi le a l r e a d y an exemplary Japanese technique, i t has n o t y e t been implemented by any American p l a n t .

T h i s procedure, however, produces a l a r g e amount o f s ludge r e -

F i g u r e 3 i s t h e f l o w diagram f o r t h e NSC i o n exchange process, much s i m p l e r t han conven t iona l processes and o f f e r s seve ra l advant$ges. i n f l u e n t wa te r t o t h e i o n exchange process c o n t a i n s 50-200 ppm Fe2 and 100-500 ppm C1- i o n s . t h e c a t i o n exchange r e s i n column t o remove t h e Fe2 i n t o t h e a n i o n exchange r e s i n column t o remove C1- i o n s and o b t a i n pu re water . T h i s pure water i s t hen r e c y c l e d as r i n s e wa te r .

It i s The

T h i s r i n s e wastewater i s d i r e c t l y i n t r o d u c e d i n t o i o n s

i o n s and subsequent ly

The c a t i o n exchange r e s i n i s regenera ted w i t h h i g h l y concen t ra ted hydro- c h l o r i c a c i d and t h e regeneran t waste s o l u t i o n i s used as a supp ly o f supplementary p i c k l i n g a c i d . The a n i o n exchange r e s i n i s regenerated w i t h c a u s t i c soda and i t s regeneran t waste s o l u t i o n i s used as a fume scrubbed a b s o r p t i o n s o l u t i o n f o r h y d r o c h l o r i c a c i d p i c k l i n g o r as an a l k a l i n e d e o i l i n g s o l u t i o n p reced ing t h e p i c k l i n g process. r e s i n r e g e n e r a t i o n a r e taken from t h e e f f l u e n t ( t r e a t e d w a t e r ) ; t h e water i s mixed w i t h r ins 'e wastewater f o r i o n exchange t r e a t m e n t ,

Bo th washing and backwashing wa te r f o r

The process f e a t u r e s a r e : e

e e

The process i s c losed : no wa%er i s be ing d i scha rged from t h e system and chemicals and agents a r e e f f e c t i v e l y economized. The process does n o t produce any secondary waste such as s ludge. Because t h e process s u p p l i e s i t s own pu re wa te r as i t t r e a t s wastewater, water supp ly and d ra inage c o s t s a r e l o w e r than those o f conven t iona l throwaway systems.

T ransac t i ons o f t h e I r o n and S tee l I n s t i t u t e o f Japan, Vo l . 17, No. 8, 1977, 8

pp. 437-438 ' P r i v a t e communication f rom Nippon S tee l Corpo ra t i on . P l a n t and Machinery D i v i s i o n , Eng ineer ing D i v i s i o n s Group on Nippon S t e e l ' s I o n Exchange Resin Method f o r P i c k l i n g Rinse Wastewater Treatment.

Brochure f rom NSC's

12

I IStorage Tank 1 j ( p ~ control) /

I I 1

change Column 1 i I

1 j j

I i (regenera tion)

!

+ /E f f luen t Tank I

To Pickling Tank - - - HCI ---

To Fume Scrubber, e t c . - - - NoOH - - -

F I G U R E 3. NIPPON S T E E L CORPORATION I O Y EXCHANGE PROCESS

o The process operates a u t o m a t i c a l l y , r e d u c i n g l a b o r requ i remen ts . e Because wa te r i s r e c y c l e d , e f f e c t i v e wa te r r e s o u r c e u t i l i z a t i o n

i s assured. e I n conven t iona l processes, r i n s e water i s heated before r i n s i n g

begins. I n t h i s new process, wa te r h e a t i n g energy requi rements a r e reduced. The process o b t a i n s pu re wa te r as i t s e f f l u e n t and r e c y c l e s i t as r i n s e water , which i n t u r n improves r i n s i n g e f f i c i e n c y .

0

Nippon S t e e l Corpo ra t i on t r e a t s r i n s e wastewater f rom t h e a c i d p i c k l i n g

The commercial s e c t i o n o f i t s K i m i t s u Works by i o n exchange f o r purposes o f env i ronmenta l p r o t e c t i o n , water resource economizat ion, and c o s t reduc t i o r , . p l a n t began o p e r a t i o n s i n 1975.

S tee l Corpo ra t i on : The f o l l o w i n g a r e t h e o p e r a t i n g da ta f rom t h e K i m i t s u Works of Nippon

I n f l u e n t f l o w r a t e I n f l u e n t p r o p e r t i e s

E f f l u e n t p r o p e r t i e s

Resin v o l ume

Opera t i on p r a c t i c e

60 m3/hr (max.) Fe < Z O O ppm C1 <500 ppm Fe <0.1 ppm C1 <1 .O ppm E l e c t r i c c o n d u c t i v i t y

C a t i o n Exchange Resin

Anion Exchange Resin

2 l i n e s a l t e r n a t e o p e r a t i o n F u l l au tomat i c o p e r a t i o n

<2 @mho /cm

2. 7m3x3

5. lm3x2

NSC c l a i m s t h a t d e s p i t e v a r y i n g i n f l u e n t p r o p e r t i e s , t h e e f f l u e n t q u a l i t y

Fe <0.1 ppm C1 <1.0 ppm pH -7 ( e l e c t r i c c o n d u c t i v i t y l ower t h a n lOpmho/cm.

i s ex t reme ly good and s t a b l e :

and

The e f f l u e n t i s r e p e a t e d l y r e c y c l e d as r i n s e water and i t s c l a r i t y r e s u l t s i n improved r i n s i n g as compared t o conven t iona l f i l t e r e d wa te r .

The Treatment o f Coke Oven L i q u o r 5

The f l o w c h a r t f o r t h i s process i n shown i n F i g u r e 4. h r o f coke oven l i q u o r l eaves t h e coke oven. i n t h i s s t ream i s about 6000-9000 mg N H 3 / l i t e r o f s o l u t i o n . i s f i r s t sen t t o a t a r decanter , where t h e t a r i s removed. then sent t h rough coke f i l t e r s t o t h e ammonia-water t a n k . con ten t i s reduced t o about 500-1100 q / l i t e r . removed by steam s t r i p p i n g . under s l i g h t l y a l k a l i n e c o n d i t i o n s (pH = 8 ) . n e u t r a l i z e d by H2S04.

About 80-90x103Kg/

Coke oven l i q u o r The l i q u o r i s

The c o n c e n t r a t i o n o f ammonia

The ammonia The r e s t o f t h e ammonia i s

T h i s process i n v o l v e s s t r i p p i n g t h e NH3 by steam

The COD o f t h i s steam i s about 3000 m g / l i t e r . The process stream i s t h e n

The

14

Neutralizer Coke Filter water

I n

A i r I u - I t I "XY'

/

NH3 I s Taken Out

- I I M C I I V U I C U a ~ u u y c cuui I

"p Siudge

--- * Treated Water

//N/ (To Be Recycled!

F I G U R E 4, FLOW SHEET OF WATER TREATMENT FROM COKE 9VEN

i s s e n t t o t h e a c h i v a t e d s ludge pool where t h e o r g a n i c s a r e decomposed by t h e b a c t e r i a a t 20-30 C. ceeds t o t h e t h i c k e n e r where f e r r i c c h l o r i d e (FeC13) and o t h e r c o a g u l a t i n g agents a r e added, r e d u c i n g t h e COD o f d u c t stream f rom t h i s s t e p t o 90 mg/ l i t e r . remove any suspended s o l i d s and th rough an a c t i v a t e d carbon tower t o remove any c o l o r .

o f b a c t e r i a . b i o c h e m i c a l l y o x i d i z e d by t h e a c t i v i t i e s o f t h e aerobic: b a c t e r i a i n an aera- t i o n chamber. B a c t e r i a thus f l o c c u l a t e d a r e sedimented and separated o u t as sl udge 1 eav i ng t r e a t e d water .

u n i t i s u s u a l l y annexed t o t h e system t o e l i m i n a t e a p a r t o f t h e o r g a n i c phase which i nc reased as a r e s u l t o f b a c t e r i a l m u l t i p l i c a t i o n . ” o f t h e s ludge i s r e c y c l e d t o m a i n t a i n some b a c t e r i a l a c t i v i t y .

The p roduc t s t ream f rom t h e a c t i v a t e d s ludge pool p ro -

From t h i s p o i n t , t h e p roduc t stream f l o w s th rough sand f i l t e r s t o

The a c t i v a t e d s ludge process i n v o l v e s an a e r o b i c r e a c t i o n i n t h e presence The o r g a n i c contaminants c o n t a i n e d i n t h e wasteware a r e

To ensure a p roper ba lance i n t h e t rea tmen t process, a s ludge d i s p o s a l

A p o r t i o n

The f o l l o w i n g o p e r a t i o n s da ta were o b t a i n e d f o r a s ludge d i s p o s a l u n i t :

I n i t i a l F i n a l

COD 3000 mg/ l 13 mg/ l NH 3 6000-9000 mg/ l 0 mg/l

The compos i t i on of t h e e f f l u e n t stream f rom t h e process i s as f o l l o w s :

TSS = 5-12 mg / l pH = 6 .6 t o 7 .1 N-Hexane = < 3 mg/ l Phenol = <0.05 mg / l

Th i s process i s u s u a l l y s p l i t i n t o two p a r t s AB and BC, as rep resen ted i n t h e f l o w c h a r t , The second p a r t o f BC removes c o l o r . p l a n t s u s i n g t h e process implement o n l y t h e f i r s t p a r t , AB. S ince a l l t h e water recovered i s used f o r process purposes, c o l o r would n o t cause problems.

Most Japanese

‘Brochure o f Japan Gasol i n e Company (JGC C o r p o r a t i o n ) , a s p e c i a l i z e d water p l a n t eng inee r ing company.

1 6

SECTION 5

THE WESTERN EUROPEAN STEEL INDUSTRY

The i r o n and s t e e l i n d u s t r y i n t h e U n i t e d Kingdom, West Germany, I t a l y , and Spain, and Belgium was examined.

The B r i t i s h S t e e l I n d u s t r y

The B r i t i s h S t e e l Corpo ra t i on (BSC) i s t h e l a r g e s t i r o n and s t e e l manu- f a c t u r e r i n t h e U n i t e d Kingdom. For a BSC p l a n t which produces 15*9x109K / r o f p f q i r o n and 24*2x109Kg/yr o f c rude s t e e l , t h e wa te r i n t a k e i s 2 .43~10 m / day.

3 . y

Table 3 shows t h e d i s t r i b u t i o n o f wa te r i n t a k e on a percentage bas is .12

Where i n d u s t r i e s a r e l o c a t e d c l o s e t o t h e coas t , t h e t i d a l waters (non-

The degree o f r e c y c l i n g v a r i e s f rom f r e s h w a t e r ) can be used. r e c y c l e d and reused t o a g r e a t e x t e n t . 2 .6 pe rcen t f o r p l a n t s u s i n g t i d a l water t o 97.8 pe rcen t f o r p l a n t s a t i n l a n d works. The v a r i o u s e f f l u e n t c o n t r o l techniques used f o r d i f f e r e n t process streams a r e d iscussed i n t h e f o l l o w i n g sec t i on . "

Fresh water , which i s c o m p a r a t i v e l y scarce, i s

Coke Ovens and Byproducts Wastes

The d i s p o s a l o f t hese wastes, pa r t i cu la , r l . y t h e spent ammoniacal l i q u o r , These e f f l u e n t s amount t o about 6500 ppm o f

Table

i s a v e r y d i f f i c u l t problem. coa l ca rbon ized and c o n t a i n s u b s t a n t i a l amounts o f t o x i c compounds such as phenols, t h iocyana tes , t h i o s u l f a t e s , c h l o r i d e s , and f i x e d ammonia. 4 g i v e s t h e approximate compos i t i on of spent ammoniacal l i q u o r o b t a i n e d i n BSC p l a n t s .

' I S p e i g h t , G.E., Davis, C.M., "A Review o f Water Supp l i es and E f f l u e n t D i s - posal , I ' unpubl ished works, p r i v a t e communication f rom D r . R . L. Cooper o f t h e B r i t i s h C a r b o n i z a t i o n Research A s s o c i a t i o n (BCRA) . T h i s work i s based on a survey o f water usage o f BSC, 1968-69. "Cook, G.W. , "Conservat ion o f Water by Reuse a t t h e Appleby-Frodingham S tee l Works, Scunthorpe," I r o n and S t e e l I n t e r n a t i o n a l , October, 1974, pp. 393-402, Table on p. 394.

17

TABLE 3

DISTRIBUTION OF WATER INTAKE - BSC (Appleby Frodingham) FOR THE YEAR ENDING MARCH, 1976 - (FORECASTED ESTIMATE)”

PROCESS

S i n t e r P1 a n t s

B l a s t Furnace Cool i n g

B l a s t Furnace Gas C lean ing

B l a s t Furnace B low ing

Coke Ovens

Stee lmak ing - BOF

Con t i nuous Ca s t i ng

R o l l i n g M i l l s

E l e c t r i c a l Power Genera t ion

Steam R a i s i n g

Domestic Purposes

S1 ag Quenching

M i sce l 1 aneous Users

% OF TOTAL WATER INTAKE

9.3

10.2

6.4

10.8

14.7

6.2

4.2

6.6

5 . 1

12.0

4.2

4 - 4

5.9

100.0%

Repr in ted w i t h pe rm iss ion ’ * I r o n and S t e e l I n t e r n a t i o n a l , October, 1974, pp. 394.

18

TABLE 4

APPROXIMATE COMPOSITION OF SPENT AMMONIACAL LIQUOR I N BRITISH STEEL CORPORATION PLANTS

CONSTITUENT PI?!! T o t a l Phenol s 1500 Thiocyanate 250 Th iosu l phate 350 C h l o r i d e 3000 Ammonia (F ree ) 2 50 Ammonia ( F i x e d ) 1200

The b i o l o g i c a l o x i d a t i o n process ( a c t i v a t e d s ludge) i s q u i t e f r e q u e n t l y used f o r t h e d i s p o s a l o f t hese e f f l u e n t s . Under f a v o r a b l e c o n d i t i o n s - - n o heavy i n f l u x , no sudden v a r i a t i o n s i n temperature, a v e r y l a r g e r e t e n t i o n t ime- - t h e process comp le te l y e l i m i n a t e s phenols and over 70 pe rcen t o f t h e t h i o - cyanate and t h i o s u l p h a t e p resen t . However, t h e s tandard a c t i v a t e d s ludge t rea tmen t process does n o t a f f e c t t h e f i x e d ammonia c o n t e n t . t rea tmen t i s necessary i f t h e s tandard a c t i v a t e d s ludge t r e a t m e n t process i s used.

Thus, f u r t h e r

B l a s t Furnace Gas Washing Waters

The amount o f s o l i d s c o l l e c t e d i n wash wa te r (suspended s o l i d s ) can be as h i g h as 4000 ppm, s e t t l e m e n t and t h i c k e n i n g .

These s o l i d s a r e u s u a l l y separated as s ludges a f t e r

The presence o f cyanides and z i n c , which a r e evolved f rom t h e b l a s t f u rnace and a r e c o l l e c t e d i n t h e washing waters , poses a d d i t i o n a l problems. The l e v e l o f these p o l l u t a n t s a r e so h i g h t h a t t h i s water cannot be d ischarged. The water i s u t i l i z e d i n some BSC p l a n t s , however, f o r e v a p o r a t i v e reuse such as s l a g quenching o r s i n t e r c o o l i n g .

Fume Cleaning f rom Oxygen S tee lmak ing

The amount o f fume f rom such oxygen s tee lmak ing processes as t h e LD conver ted, Kaldo, r o t o r , and e l e c t r i c a r c processes i s s u b s t a n t i a l - - 32-5 - 43.4 x 10-3Kg/Kg o f s t e e l , and t h e c o n c e n t r a t i o n o f s o l i d s i n t h e washing water i s o f t e n up t o about 10,000 ppm. sed imen ta t i on and f i l t r a t i o n u n i t s f o r t h e s e p a r a t i o n o f t h e i r o n o x i d e s l udges a r e normal l y employed.

R e c i r c u l a t o r y systems w i t h

Hot R o l l i n g

The main contaminants he re a r e m i l l s c a l e , o i l s , greases, and s ludges. C i r c u l a t a r y systems a r e used w i t h s c a l e p i t s , s e t t l i n g ponds, and o i l skimming f a c i l i t i e s f o r t h e coa rse r m a t e r i a l s and c l a r i f i c a t i o n and f i l t r a t i o n u n i t s f o r f i n a l c l e a n s i n g o f water b e f o r e reuse. Some o f t h e BSC p l a n t s use a

1 9

purge d i scha rge which c o n t r o l s b u i l d - u p o f d i s s o l v e d s a l t s i n t h e c i r c u l a t i n g water .

A c i d P i c k l i n g S o l u t i o n s

These pose a v e r y d i f f i c u l t e f f l u e n t problem. N e u t r a l i z a t i o n o f t h e s u l f u r i c a c i d s o l u t i o n s w i t h l i m e had been p r a c t i c e d , b u t t h i s i s an expensive process, and i t i s d i f f i c u l t t o d i spose of t h e s ludge produced. r e c o v e r y and r e g e n e r a t i o n processes have been g i v e n more impor tance. forms o f a c i d r e c o v e r y processes, based on t h e p r e c i p i t a t i o n o f f e r r o u s s u l f a t e heptahydrate o r monohydrate w i t h consequent enr ichment o f t h e a c i d c o n t e n t o f t h e rema in ing l i q u o r have been p r a c t i c e d .

Hence, a c i d Severa l

A l though s u l f u r i c a c i d p i c k l i n g i s s t i l l b e i n g w i d e l y p r a c t i c e d , t h e t r e n d i n t h e B r i t i s h s t e e l i n d u s t r y has been towards h y d r o c h l o r i c a c i d p i c k l i n g combined w i t h r e g e n e r a t i o n o f t h e a c i d f rom t h e spent l i q u o r . BSC has one o f t hese p l a n t s c u r r e n t l y under o p e r a t i o n , and q u i t e a few more a r e under c o n s t r u c t i o n .

Cold R o l l i n g

The wastes f rom c o l d r o l l i n g a r e contaminated w i t h r o l l i n g o i l s , d e t e r -

The stream l e a v i n g t h i s s t e p i s a c i d i f i e d w i t h spent p i c k l e l i q u o r gents, and m e t a l l i c p a r t i c l e s . The e f f l u e n t s a r e i n i t i a l l y skimmed and s e t t l e d . o r an a c i d i c r i n s e water t o break down t h e emulsions. The f r e e o i l i s t hen skimmed o f f and , t h e rema in ing 1 i q u o r n e u t r a l i z e d and c l a r i f i e d .

Table 5 g i v e s t h e maximum p e r m i t t e d e f f l u e n t l e v e l s o f t o x i c c o n s t i t u e n t s f rom b l a s t f u rnace gas c l e a n i n g wa te r r e c y c l i n g systems. t h e Appleby-Frodingham works o f t h e B r i t i s h S tee l Corpo ra t i on .13

The da ta i s f rom

TABLE 5

BLAST FURNACE GAS CLEANING SYSTEMS - MAXIMUM CONCENTRATION OF TOXIC CONSTITU- ENTS I N TREATED EFFLUENT WATER13

CONSTITUENT I MAXIMUM CONCENTRATION - Mg/ l

Suspended s o l i d s D isso lved s o l i d s as f l u o r i d e D i s s o l v e d z i nc o r 1 ead Free cyanide

30.0 25.0 1 .o 0.1

Repr in ted w i t h pe rm iss ion . 13C00k, G.W. , "Conservat ion of Water by Reuse a t t h e Appleby-Frodingham S t e e l Works, Scunthorpe," I r o n and S t e e l I n t e r n a t i o n a l , Oc tober ' 1974, pp. 401 Table on 401.

20

The Appleby-Frodingham Works o f British Steel C o r p o r a t x

The Appleby-Frodingham Works i n Scunthrope i s considered t o be a wor ld leader i n steelmaking e f f i ~ i e n c y . ' ~ The extent of water reuse here has been s t e a d i l y increasing. Between 1972 and 1976 t h e t o t a l consumption expressed a s Kg o f water/Kg o f s t e e l has decreased from 4.94 t o 2.74, Dur ing t he same period, the s t ee l output has increased from 1.44 x l o 9 Kg t o 4:50 x lo9 Kg. The Appleby-Frodingham Works uses pnysical , chemical , and biological methods of treatment e i t h e r separa te ly o r i n conjunction w i t h each o ther .

P hys ica 1 Treatment - - The water from the primary sca l e s e t t l i n g pits i s lead t o four rectangu-

The f i l t e r s , designed for h i g h s p e c i f i c l a r c l a r i f i e r s , each equipped w i t h a t r ave l ing bridge sc rape r , and then t o 1 2 horizontal sand pressure f i l t e r s , f i l t r a t i o n r a t e s of 14.8 t o 1 6 . 0 m 3 / m 2 / h r , operate and clean automatical ly . The suspended so l id s content o f the wateg i s reduced t o not more than 5 ppm. The f i l t e r e d water i s cooled t o below 29 C i n a th ree-ce l l open evaporative cooling tower before b e i n g r ec i r cu la t ed .

C hem i cal Treatment - - The water used fo r b l a s t furnace gas cleaning i s t r ea t ed by a chemical

process. This stream contains not only d u s t p a r t i c l e s , b u t a l s o contaminants such as z inc , l ead , cyanide, and f luor ide . Table 6 gives an ana lys i s of the r ec i r cu la t ing water i n t he b l a s t furnace gas cleaning system. Figure 5 shows the flow diagram of this chemical process.

T A B L E 6

ANALYSIS OF RECIRCULATING WATER IN BLAST FURNACE GAS CLEANING SYSTEM AT APPLEBY -FRODI N G H A M ~

CONSTITUENT

PH Suspended s o l i d s Dissolved f luo r ide D i ssol ved zinc Dissolved 1 ead Free cyanide

V A L U E

8.4 30.0 mg/l 85.0 mg/l 10.0 mg/ l 4.0 mg/ l

10.0 mg/l

From Iron and Steel Internat ional , October 1974, p p . 401, Table 4

Reprinted w i t h permission 14"Appleby and Frodingham from the 1860's t o the 1 9 7 0 ' ~ ~ ' ' Steel Times, Vol . 203, No. 6 , June, 1975, pp . 407-498.

21

Sulphuric

Iu N

Lime n Silo

To I Pian t

Sludge Disposal

dash vlatrr

IN

Treated Ef f iuent Disc ha r g e

Figure 5.Eff luent treatment process for removal of l ead , z inc , f lou r ide and f r e e cyanides

Reprinted w i t h permission Steel Times, June 1975,p496

Lime i s added t o the incoming l iquor t o r a i s e i t s pH t o between 1 1 . 9 a n d This a l k a l i n e condition i s necessary f o r the oxidat ion of t he cyanide

Chlorine 12 .2 . and the prec ip i ta t ion of the z inc , l ead , and most of the f luo r ide . i s in jec ted a s t he l i quor enters a ' c i r c u l a t o r ' reactior)/sedimentation tank which i s designed t o give int imate mixing of t h e chemicals w i t h the l iquor and allow adequate time for subsequent s e t t l i n g o f the p rec ip i t a t e s . p rec ip i ta ted s o l i d s a r e withdrawn a s a sludge which i s returned t o the b l a s t furnace gas cleaning s l u r r y lagoon. The c l a r i f i e d water from the c i r c u l a t o r i s fed t h r o u g h pressure sand f i l t e r s t o a neu t r a l i za t ion tank where s u l f u r i c acid i s added t o r e s t o r e the pH value t o between 5 and 9. acid s torage tank, f i l t e r wash water tank, and cont ro ls permit the p lan t t o be self-contained and automatic i n i t s operat ion. th is process meet t he standards shown i n Table 5 .

The

The lime s i l o ,

The e f f luen t s leaving

Biological Treatment--

Appleby-Frodingham Works uses a cent ra l plant f o r the biological t r e a t - ment of t he e f f l u e n t from th ree coke oven plants and two t a r d i s t i l l a t i o n p lan ts . i n a r e se rvo i r w i t h a capaci ty o f 3180 m 3 located a t t he treatment p l an t . T h i s l iquor i s d i lu t ed by adding a maximum of 0.71 m 3 / m i n of ' c l ean ' drainage.

The mixed l iquor from the r e se rvo i r i s fed i n t o nine aera t ion c e l l s , each f i t t e d w i t h a sur face ae ra to r . and so l id s removal, the nine c e l l s a r e operated a s t h ree stream flows t o a separa te c l a r i f i e r so t h a t under normal opera t ion , biological sludge i s returned only t o those c e l l s serving the pa r t i cu la r c l a r i f i e r .

The e f f luen t s , t o t a l l i n g an average of 3.075 m 3 / m i n , a r e co l lec ted

For the purpose of sludge r ec i r cu la t ion

The supernatant l i q u o r from the c l a r i f i e r s flows by gravi ty t o a t i d a l s torage r e se rvo i r of 3200 m 3 capaci ty before discharge.

The Other Western European Works

Information a s de ta i led a s t h a t obtained from Japan and Br i t a in was not access ib le from other Western European count r ies . The problems were primarily caused by a language b a r r i e r , plus a hesitancy of plant o f f i c i a l s t o discuss the possi 'b i l i ty o f po l lu t ion . The information presented here i s e s s e n t i a l l y from published l i t e r a t u r e ava i l ab le i n t h e English language.

West Germany

German pol lut ion control investments have been climbing sharply i n t he l a s t few years . Between 1961 and 1970, 7.3 percent of t o t a l cap i t a l investment of the German s t e e l industry was a l loca ted t o pol lut ion con t ro l . fo r 1973 indica te the pol lut ion control investment t o be around 1 2 percent. Between 1969 and 1971, the amount expended by the s t e e l and metal working industry f o r investment maintenance and research represented i n the aggre a t e

I5Theegarter, H.F. , Von Hartman, R . K . , "Hoesch Huttenwerke's Hot S t r i p Mill Water Supply System," Iron and Steel Engineer, A u g u s t , 1973, p p . 67-74.

Figures

34.4 percent of a l l monies spent by German indus t ry on pol lut ion con t ro l . 9 5

23

The data i n Table 7 rep resen t West German e f f l u e n t g u i d e l i n e s as o f 1973.

TABLE 7

PERMISSIBLE I M P U R I T I E S I N INDUSTRIAL WASTE WATER'

Temperature O C S e t t l i n g m a t e r i a l s , ppm A c i d i t y , pH T o t a l Chromium ppm Copper Y PPm N i c k e l , ppm Zinc, ppm T o t a l i r o n , ppm

Cyanides, ppm O i l , ppm

Repr in ted w i t h e rm iss ion I 5 I r o n and S tee l F ng ineer , August, 1973, pp

30 1 .o 6.5-9.5 4.0 3.0 590 5.0 No l i m i t a t i o n s i f no problems w i t h t rea tmen t a r e t o be expected. 1 .o 0.0

67

I t i s understood t h a t t h e German a u t h o r i t i e s a r e c u r r e n t l y s e t t i n g up even more s t r i n g e n t g u i d e l i n e s . were unab le t o g e t any s p e c i f i c i n f o r m a t i o n on t h e newer g u i d e l i n e s .

U n f o r t u n a t e l y , d e s p i t e repeated requests , we

I t a l y

L I t a l y , 1 i quor I s a l s across

Spain

ke t h e Japanese and B r i t i s h p l a n t s , t h e I t a l s i d e r p l a n t a t Taranto, a l s o uses a l a r g e amount o f sea water . by means o f ammonia s t r i p p i n g and t h e b i o l o g i c a l o x i d a t i o n process.

t h e water o u t l e t channel t o remove o i l f i l m s . I 6

The p l a n t t r e a t s coke oven

uses an i n t e r e s t i n g techn ique: i n f l a t a b l e c o l l a r s a r e fas tened

The S p a n i s h ' p o l l u t i o n c o n t r o l g u i d e l i n e s da te back t o 1961. A t t h e i n t e g r a t e d p l a n t a t Sagunto considered, g r e a t a t t e n t i o n i s p a i d t o keeping p o l l u t i o n t o a minimum.

I t i s i n t e r e s t i n g t o n o t e t h a t a l t hough some research and development i s c a r r i e d ou t , r e l i a n c e on f o r e i g n 'know-how' i s s t i l l s t rong .17

I6VandenBerge, H., "Ana lys i s , Measurement and Con t ro l a t I t a l s i d e r , Taranto," {yon and S tee l I n t e r n a t i o n a l , Vol 49 , No, 5, October, 1976, pp.325-336.

Richard, R.A.C., "The R ise o f t h e Spanish S t e e l Indus t ry , ' ' I r o n and S tee l I n t e r n a t i o n a l , Vol 47, No. 5, October, 1976, pp.353-360.

24

Bel gium

March, 1971, w i t h r e v i s i o n s i n August, 1974 and August, 1976, The f o l l o w i n g e f f l u e n t g u i d e l i n e s f o r fe r rous me ta l i n d u s t r i e s rep resen t maximum a d d i t i o n s which can be made t o e x i s t i n g l e v e l s i n t h e source wa te rs , g u i d e l i n e s of August 3, 1976, a f fec ted s t e e l p l a n t s , c a s t i r o n foundr ies , h o t r o l l i n g , and s i m i l a r s p e c i a l i t y works t h a t were o u t o f compliance:

Be lg ium's water p o l l u t i o n c o n t r o l g u i d e l i n e s da te back t o l e g i s l a t i o n o f

The s p e c i f i c

1. 2.

3 .

F i v e (5 ) day Bas ic Oxygen Demand (BOD), 20°C; l e s s than 30 mg/ l . Temperature L i m i t s , " s l a g g r a n u l a t i n g ' ' as a separa te d ischarge, l e s s than 35 C. For h o t r o l l i n g and s p e c i a l i t y s t e e l works, l i m i t s f o r separa te d i scha rge o n l y : a ) pe t ro leum e t h e r e x t r a c t i o n : 20 m g / l b ) a p o l a r i t y s o l i d s by carbon t e t r a c h l o r i d e e x t r a c t i o n ,

c o l d water : 1 5 mg/l

Fur the r g u i d e l i n e s r e v i s i o n s c i t e d i n August, 1976 g i v e t h e f o l l o w i n g maximums:

1. 2. 3. 4. 5. 6. 7. 8.

Cyan i de (-ox i d i zed by c h l o r i na t i on ) Chemical Oxi en Demand (COD)

S U I f a t e s ( S o b )

T o t a l Z inc T o t a l l e a d D i l u t e d i r o n D i l u t e d manganese

F l u o r i d e (F- 7 0.5 mg/l

500.Q mg/l 1 0 ' 0 mg/l

2000 ,O mg/l 5.0 mg/l 1.0 mg/l 2.0 mg/l 1.0 mg/l

These s tandards were proposed f o r a f i v e yea r pe r iod , t o 1981; t h e y were pub l i shed September 29, 1976, i n t h e B e l g r i s c h S t a a t s b l a d ( t h e B e l g i a n M o n i t o r ) , a government pub1 i c a t i o n .

25

APPENDIX A

SOURCES OF INFORMATION

Data fo r this project were obtained by: 1. Manual searches i n l i b r a r i e s , 2 . Computerized searches, 3 . Telephone interview a n d TELEX,

The data bases t h a t were searched t h r o u g h our Computer Search Center were :

APTIC: A comprehensive resource on a l l aspects of a i r po l lu t ion ,

BIOSIS PREVIEWS: Citat ions on a l l aspects of t he biosciences a n d i t s e f f e c t s , prevention, and con t ro l .

medical research. CA CONDENSATES: L i te ra ture on chemistry, chemical engineering, and

chemical aspects of t he l i f e sciences. CHEMICAL INDUSTRY NOTES (CIN) : Art i c l e s from over 75 worldwide business-

or iented per iodicals which cover the chemical processing indus t r i e s .

t ions of engineering s o c i e t i e s , proceedings of conferences, a n d selected government repor t s and books.

national primary and secondary source publ icat ions report ing on a l l aspects of the environment.

from approximately 250 journals throughout t he world.

the science a n d prac t ice of metallurgy produced by the American Society f o r Metals (ASM) and the Metals Society (London). Government-sponsored research, development, and engineering plus analyses prepared by federal agencies , t h e i r cont rac tors , or grantees.

Environmentally-related l i t e r a t u r e on pol lu t ion , i t s sources and cont ro l .

Mu1 t i d i s c i p l inary index to the 1 i t e r a t u r e of science and technology, containing 90 percent of t he world's s i g n i f i c a n t s c i e n t i f i c a n d technical l i t e r a t u r e .

descr ipt ions on ongoing research i n a l l a reas of research.

COMPENDEX I Worldwide coverage o f approximately 3,500 journal s , pub1 ica-

Indexing and abs t rac t ing coverage of more than 5,000 i n t e r - ENVIROLINE:

ISMEC: Abstracts of s ign i f i can t a r t i c l e s i n mechanical engineering

METADEX (Metals Abstracts/Al loys Index) : Internat ional 1 i t e r a t u r e on

- NTIS:

POLLUTION ABSTRACTS:

SCISEARCH:

SSIE (Smithsonian Science Information Exchange) : Abstracts and project

26

The f o l l o w i n g i s a l i s t o f o r g a n i z a t i o n s con tac ted :

Cent re f o r Techn ica l and S c i e n t i f i c I n f o r m a t i o n and Documentation (TNO) , D e l f t , Nether lands U n i t e d Kingdom Chemical I n f o r m a t i o n S e r v i c e Danmarks Tekn iske B i b l i o t e k , Denmark Royal I n s t i t u t e o f Technology L i b r a r y , Sweden The Japan I n f o r m a t i o n Center o f Sc ience and Technology, Japan K inokun iya Book-Store Company, Tokyo I r o n and S t e e l Federa t i on o f Japan I n t e r n a t i o n a l I r o n and S t e e l I n s t i t u t e , Belg ium Umwel tbundesamt (Federa l Envi ronmenta l Agency) a B e r l i n I W .Germany Nether lands Consul Genera l , Chicago, I L , U,S,A. German Consul General, Chicago, I L , U,S.A. I t a l i a n Trade Commissioner, Chicago, IL,U,S.A: Chamber o f Commerce, Luxemburg City, Luxemburg Swedish Counsul General, Chicago, I L U.S.A. J.G.C. Corpo ra t i on , Tokyo, Japan Nippon S t e e l Corpo ra t i on , Tokyo, Japan Nippon Kokan Corpo ra t i on , Kawasaki , Japan Krupp I n d u s t i r e s and S t e e l Works, Essen, Germany Emiss ion Techn ica l I n s t i t u t e , Baden-Baden, W . Germany Water P o l l u t i o n Research Lab., Stevenage, H e r t s , England B r i t i s h S t e e l Corpo ra t i on , Middlesbourgh, Cleveland, U n i t e d Kingdom B r i t i s h C a r b o n i z a t i o n Research Assn., Wingerwor th.Chester f ie ld , Derbysh i re , U n i t e d Kingdom The M e t a l s S o c i e t y , London, U n i t e d Kingdom A1 k a l i d e I n s p e c t o r a t e , U n i t e d Kingdom Hydro techn ics , I n c . , New York, NY, U.S.A. Eng ineer ing Science, I n c . , A u s t i n , TX, U . S . A . Department o f t h e Environment, Water D i r e c t o r a t e , London, U n i t e d Kingdom Aquatechnics, Chicago, IL,U.S.A. Gurnham Assoc ia tes , Chicago, I L , U.S.A. S t a n l e y Consu l tan ts , Muscat ine, I A , U.S.A. Hydro Science, I n c . , Westward, NJ, U.S.A.

S i t e s v i s i t e d :

0 I n l a n d S t e e l , Eas t Chicago, I N , U.S.A. e Hydro techn ics , I nc . , New York, NY, U.S.A. 0 Belg ium Consulate, Chicago, I L , U.S.A.

A genera l b i b l i o g r a p h y i s found i n Appendix B .

27

APPENDIX B

GENERAL BIBLIOGRAPHY

1.

2.

3.

4.

5.

6.

7.

8.

9.

10.

11.

12.

13.

14.

" A c i d Regenerat ion Goes Remote," 33 Mazazine, March 1973,

" A c t i v a t e d Carbon Makes Water C1eanatJ E n v i r . S c i . and Tech, Vol 10, No. 10, October 1976.

"Anchor and t h e Environment," I r o n and S t e e l , S p e c i a l I ssue , A p r i l 1974.

"Appleby and Frodingham from t h e 1860s t o t h e 1 9 7 0 ~ ~ " S t e e l Times, Vo l . 203, No. 6, June 1975.

"Armco Takes F o r e f r o n t i n B a t t l e A g a i n s t A i r and Water P o l l u t i o n , " 33 Magazine, June 1973.

N E I C - " C h a r a c t e r i z a t i o n and E v a l u a t i o n o f Wastewater Sources," U.S. S t e e l Corp., I r v i n P l a n t , P i t t s b u r g h , PA, Aug. 18-28, 1975, December 1975.

N E I C - " C h a r a c t e r i z a t i o n and Eva1 u a t i o n o f Wastewater Sources ,It U.S. S t e e l Corp. Homestead Wheel and A x l e P l a n t , McKees Rocks, PA, August 21-28, 1975, January 1976.

" C u r r e n t Abs t rac ts , " E n v i r . S c i and Tech., Vo l , 10, No, 3, March 1976.

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129. "Environment P r o t e c t i o n Ac t , Mar ine Dumping P r o t e c t i o n A c t w i t h Commen- t a r i e s , " Brochure f rom Sweden, I n f o r m a t i o n t o U n i t e d Na t ions Conference on t h e Human Environment,

130. "The Fukuyama F i l t e r s , " Brochure f rom Hydro techn ic Corp.

131. "Management o f Land and Water Resources," Brochure f rom Sweden, I n f o r m a t i o n t o t h e U n i t e d Na t ions Conference on t h e Human Envi ronment .

132. "Nippon S t e e l ' s I o n Exchange Resin Method f o r P i c k l i n g R inse Water Treatment," Brochure f rom Nippon S t e e l Corp, (Japan).

133. " S o l u t i o n o f t h e Water Problem a t Taranto ( I t a l y ) S t e e l P lan t , " f rom Hydro t ec hn i c Corp .

134. "U1 t r a - H i g h Rate F i l t r a t i o n , A New Technique f o r P u r i f i c a t i o n s and Reuse o f Water," f rom Hydro techn ic Corp.

135. "Water f o r a Growing G ian t - Nippon Kokan's Fukuyama Works," f rom Hydro t e c hn i c Corp.

136. "Water Treatment ,I' b rochure f rom JGC Corp., (Japan) .

36

TECHNICAL REPORT OATA (Please read Inrtnrchons on the reverse be fore completing)

1 . REPORT NO. 12. 13. RECIPIENT'S ACCESSION NO.

Review of Western European and Japanese Iron and Steel Industry Exemplary Water Pollution Control Te chnolov

H. M. Tockmam, G. Swaminathan, and J. D. Stockham

lIT Research Institute

7. AUTHOR(S)

3. PERFORMING OROANIZATION N A M E A N D ADDRESS

10 West 35th Street Chicago, Illinois 60616

EPA-600/2-79-002 I I 4. TITLE A N D SUBTITLE 16. REPORT D A T E

January 1979 6. PERFORMING ORGANIZATION CODE

8. PERFORMING ORGANIZATION REPORT NO

10. PROGRAM ELEMENT NO.

1BB610 11. CONTRACT/GRANT NO.

68-02-2617, Task 2-3 12. SPONSORING AGENCY N A M E A N 0 ADDRESS

EPA, Office of Research and Development Industrial Environmental Research Laboratory

13. TYPE OF REPORT A N D PERIOD COVERED

Final; 8/77 - 1/78 14. SPONSORING AGENCY CODE

Research Triangle Park , NC 27711 15.SUPPLEMENTARY

919/541-2 733.

I EPA/600/13 IERL-RTP project officer is John S. Ruppersberger , MD-62,

16. ABSTRACT The report gives results of a literature survey of current Western Euro- pean and Japanese water pollution control technology in the iron and steel industry. Further informatioo was obtained through personel communication. Recycle technology was identified as being practiced to a high degree by the Japanese. A variable recycle rate w a s found to be practiced at British and Western European s teel plants. Summaries of typical pollution control operations are described and comparative date are provided.

,7 . K E Y WORDS A N D DOCUMENT ANALYSIS

I. DESCRI PTORS

Water Pollution Iron and Steel Industry Industrial Processes Water Re clam at ion

18. DISTRIBUTION STATEMENT

Unlimited

). I DENTI F I E RS/OPEN ENDED TERMS

Water Pollution Control Stationary Sources Europe Japan

19. SECURITY CLASS (This Report).

EO. SECURITY CLASS (Thispage) Unclassified Unclassified

:. cOSATI Fleld/Group

13 B 11 F 13 H

21. NO. OF PAGES 44

22. PRICE

37 !PA Form 2220.1 (B-73)

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