ILLINOIS POLLUTION CONTROL BOARD

December 6, 1973

UNION OIL 

COMPANY

OF CALIFORNIA

CHICAGO REFINERY

PETI TIONER

PCB 72—447

ENVIRONMENTAL PROTECTION AGENCY

RESPONDENT

ARTHUR T~ LENNON, ATTORNEY, in behalf of UNION OIL COMPANY

DENNIS R. FIELDS, ASSISTANT ATTORNEY GENERAL, in behalf of the

ENVIRONMENTAL PROTECTION AGENCY

OPINION AND ORDER OF THE BOARD (by Mr. Narder)

This action involves a variance request filed by 

Union 

Oil

Company on November 6, l972~ Relief was sought from Rules 408, 1002

of Chapter 3 of the Water Pollution Regulations of Illinois and Rule

1.07-10 (c) of SWB—15. Variance would allow Petitioner to exceed

the 0.025 mg/i standard as it applies to cyanide concentrations.

Union Oil Company of California owns and operates, in Lemont

a major oil refinery. This refinery processes approximately

148,000 barrels of crude oil per day, and had a base cost of over

two hundred and fifty million dollars.

The main units of this operation are cokers and fluid catalytic

cracking (F.C.C.) units which are used to produce gasoline and other

usable products from incoming crude oil. Both units raise the temp-

erature of the incoming crude oil to about 900 degrees. This causes

the high molecular weight substance to break down or “crack” to form

the usable products. It is during this cracking that some of the re-

suiting atoms form the cyanide ion. It has been found (H. 151) that

much more cyanide is formed in the F.C.C. than in the coker units.

The products manufactured at the Chicago refinery range the en-

tire gamut of hydrocarbons starting from the light gases 

(

e.g.,

methane, ethane) to propane to gasoline. A large amount of both al-

iphatic and aromatic solvents are also manufactured. Heating oils of

all grades (No. 

4, 6) as well as the residual tars used for asphalt

are produced. Cove and sulphur are the other Droducts produced.

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As part of the variance petition, Petitioner included an Interim

Report on Evaluation of Cyanide Problems at Union Oil Company of Cal-

ifornia’s Chicago Refinery. This report outlined the potential sourc-

es and methods of cyanide removal. The Agency filed its original

recommendation on December 22, 1972, in which it recommended a denial.

On April 17, 1973, after the use of several discovery devices and

meeting with the Petitioner, the Agency amended its recommendation.

In its amended recommendation the Agency recommended a grant of vari-

ance subject to certain conditions. Hearings were held on June 4,

1973, in Romeoville, Illinois. At these hearings much technical in-

formation concerning the problems with cyanides was elicited. It is

noted that the Respondent made no opening or closing statement at

hearing and no witnesses were called at the hearing by the Respondent.

The only evidence entered at the hearing by Respondent was the full

text of its recommendation. This is particularly important in that

Petitioner elicited testimony from a number of expert witnesses and

all of this testimony was in essence unrebutted.

On October 18, 1973, the Board issued an order for more informa-

tion. This order was an attempt to bring up to date the status of

Petitioner’s attempts to abate its cyanide levels. An updated sec-

ond interim report was received and made part of the record.

Present Status of Petitioner’s Effluent

The present regulation 1.07-10 (c) of SWB—l5 will be replaced by

Rule 408 (a) of Chapter 3: Water Pollution Regulations of Illinois

on December 31, 1973. Both of these rules require an effluent con-

centration of no more than 0.025 mg/i of cyanide. The following is

a table showing Petitioner’s effluent loading:

1972

1973

January      

0.149 mg/i CN   

0.258 mg/i CN

February      

0.135       

0.190

March       

0.075  

“

0.226

April       

0.074       

0.167

May

0.102  

“

0.129

June        

0.225  

“

0.045

July        

0.136  

“

0.044

August       

0.097  

“

0.078

September     

0.087  

“

0,054

October      

0.075

November     

0.165

December      

0.251

Although on the surface it would seem that the cyanide level has

been decreasing, it is not clear as to whether this is due to better

processing or different feed conditions.

Petitioner has presented

evidence (second interim report) that the generation of cyanide is

highly dependent on the nitrogen loading on the crude oil feed. It is

best for the Board not to take the position that the seeming downward

trend of cyanide will continue without much additional work.

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Petitioner claims to be removing, during 1973, in excess of 95

of its incoming cyanide load. This reduction, however, is not enough

to reach the 0.025 allowable limit as dramatized in the above table.

It is alleged that notification of excessive cyanide levels was first

brought to Petitioner’s attention in May, 1971. Since then Petitioner

alleges that all possible steps were initiated to try and solve the

problem. Testimony (R. 5) was elicited that the Chicago refinery uses

much less water than do others. As a result of this water conserva-

tion program, it is alleged that the cyanide problem is magnified due

to the lack of inherent dilution effects found at other refineries of

this type.

Analytical Problems Regarding Cyanide

Much testimony was offered regarding the difficulty in obtaining

true and meaningful analytical data for cyanide at the low levels re-

quired to meet applicable standards. Petitioner is continuing to use

the Federal Environmental Protection Agency publication, Methods for

Chemical Analysis of Water and Wastes 1971, for its determination of

total cyanide in its waste water. The Petitioner still does not have

a method of determining the difference between simple and complex cy-

anide.

Alice Roketa (Manager of the Environmental Division of Arro Labs)

testified (R. 74-78) that there are three basic sources which outline

methods to determine cyanide: Standard Methods, Federal Book on Meth-

ods, and the ASTM method. These three sources generally use the same

approach of distillation and titration or colorimetric determination.

However, they do not distinguish between simple and complex cyanides.

Alfred Tenny (chemist, president of Tenco Hydro Aerosciences) test-

ified (R. 116-120) that there is significant difficulty in getting ac-

curate measurements at low levels of cyanide. As a chemist Mr. Tenny

spent three years studying cyanides and alleges that at a level of

0.02 ppm. the error would be in the order of 30 to 50 percent. He

alleges that the destruction of cyanide by catalysts and non-decomp-

osition of the complex cyanides may be two reasons for errors. He

also mentions that extremely good laboratory technique is required to

obtain consistent results.

Dr. Fred Gurnham (President of Gurnham & Associates,

Inc.) testi-

fied CR. 303-4) that he has been a member of the American Electro-

platers Society and in charge of a project on analytical techniques

for cyanide removal.

Dr. Gurnham further testified that he does

not

think that 0.025

mg/l can be accurately measured. He further testi-

fled that if 

several laboratories were to test a standard

0.2

mg/l

solution of cyanide the reports would be from 0.0 to 0.6 mg/l.

Free vs. Complex Cyanide

A great deal of testimony centered around the difference between

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free versus complex cyanides. It is alleged that the problem of com-

plex ions is one that has not been handled in the past and was not

contemplated when the original water pollution regulations were adopt-

ed. The generally accepted method of cyanide removal is the alkaline

chlorination process which has proven undesirable because of the poss—

ibilitly of toxic byproducts being formed by the interaction of ammon-

ia, cyanide, and chlorine.

The abovementioned witnesses (Roketa, Tenny, Gurnham) all testified

as to the differences between complex and simple cyanides. Witness

Roketa testified that in her readings she has found that the complex

(FE iron) cyanide is very much less toxic than is the simple (Na

çsodium, H (hydrogen) cyanide. This 

because the dissociation

comes about 

photodecomposition rather than by simple breakage of an

ionic 

bond

which 

present 

simple cyanide. Witness Tenny again

covered the difference between co—ordinate and ionic bonding and reaf-

firmed the difficulty of obtaining a free cyanide radical in a complex

ferric cyanide. Mr. Gingham discussed the above again (R. 306) and

further elaborated on the interaction 

complex and simple cyanides

when mixed in solution. He mentioned that a sodium iron cyanide is

extremely stable and that very little if any iron is free (therefore

very little free cyanide). This in the witnessts opinion 

would reduce

the toxicity of the complex to nil. He further stated that a 

standard

first aid technique for cyanide poisoning is to drink an iron salt in

hopes of complexing the free cyanide and thereby reducing toxicity.

Sunuoary of Abatement Technology Tried

Petitioner has submitted a preliminary and second interim report

on studies made to abate cyanide in its effluent stream, It is al-

leged that although these research prbjects are ongoing no satisfact-

ory method has been found.

Testimony (H. 150) was entered that the source of cyanide genera-

tion has been located in the plant. Cyanide is alleged to be found

as a byproduct in the cracking operations.

John Bernickes testified as to the status of all methods used in

the plant to abate cyanide (R. 210-261). 

This

information has been

further updated 

in the

second interim report submitted by Petitioner.

1. Carbon Adsorption: ~o pilot plant studies were conducted by

Petitio~, using the carbon adsorption method. The first pilot plant

was operated under Calgonrs guidance. This plant was run on a fairly

high cyanide concentration stream. The summary of this effort was

contained in Calgon’s report 

Petitioner. The essence of this report

was

that

the tests were unsuccessful due to the presence of the stable

ferrocyanide complex.

The second 

pilot plant was supervised

by

plant

personnel. Preliin-

mary jar tests were encouraging in 

that a carbon usage of 1,8*/bOO

gal. of water

would 

produce an effluent with negligible cyanide con-

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tent. Pilot plant data showed that approximately 11.8 lbs. of car-

bon would be required to treat 1000 gal. of water. This extrapolates

to 8,050 lbs. of carbon for each pound of cyanide removed. High vel-

ocity backwashing was used to strip adsorbed cyanide from the used

carbon in an attempt to regenerate it. This technique had some ef-

fect. Attempts to catalytically oxidize adsorbed cyanide by the pres-

ence of oxygen and copper did not prove successful. No mention is

made as to whether continuing studies are proposed as to this tech-

nique by Petitioner.

Reference (H, 172) was made to a total refinery treatment of cyan-

ide by carbon adsorption in Marcus Hook, Pennsylvania. Petitioner

makes no mention as to the results of this project in its interim re-

port. This technology could be significant to Petitioner~s problems

and should be investigated fully in any further reports by Petitioner

the Agency.

2. Chlorination: Petitioner alleges that two programs involving

chlorination were under study during the last year. Full—scale act-

ivated sludge chlorination and laboratory evaluation of alkaline

chlorination were examined. From the data presented 

it would seem

that chlorination has some merit as a cyanide reducing agent, but

that little hope of achieving the 0.025 specifications can be offered

using present techniques. Tests involving the alkaline chlorina-

tion method proved unsuccessful.

Again Petitioner makes no reference as to whether it intends 

further develop and explore this technology.

3. Incineration: This technique was deferred until such time as

the volume of water can be reduced. The Board can agree that the use

of 210 x

106 B~U/hr. for evaporation and incineration is excessive in

light of the p~oblem.

4. Polysulfide Injection:

The technique of using polysulfide to

convert cyanide to thyocyanide was explored.

It is postulated that

the thyocyanide radical will decrease the cyanide corrosion problem

and reduce the formation 

of the ferrocyanide complex. It

is

unclear

as to what the nature of

the new product formed would be, and the

problems as to its removal.

Petitioner plans

a full-scale test run which started October 23,

1973. Results should be made available in any further reports to the

Agency.

5. Precipitation:

Attempts to form an insoluble cyanide complex

have met with only moderate results.

Petitioner has

postponed the

results of this mode of testing indefinitely.

Other processes either mentioned in 

testimony

or

alluded to

in

Petitioner’s interim report include:

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A. A proprietary compound by Nalco

B. Ozonation

C. Wet oxidation

D. Peroxide treatments

Mention is made of

water reuse to bring the plant into compliance.

Petitioner indicates a degree of confidence in this technique, although

it

stipulates its confidence with a number of

assumptions. It is im-

plied that this technique will be further explored.

From the above discussion it is clear that various methodologies

are still under consideration. The summary has convinced the Board

that Union Oil is pursuing a viable program in its attempts to abate

its cyanide problem. It is also clear that Union Oil Company has not

submitted a project completion date, because it is still unsure which

technique will be satisfactory.

The nature of a project completion schedule is generally considered

to include in its body an anticipated completion date. Under normal

circumstances a variance would not be issued unless such a date is

submitted. In Mt. Carmel Public Utilities vs. Environmental Protection

Agency, PCB 71-15, the Board held:

“As a matter of policy the Board does not favor the

granting of variances without some definite assurance

that the emissions will be controlled by available

pollution control devices as soon as possible. Ex-

cept for cases of ‘no technology available’ this

Board must require that those who seek ‘a shield against

enforcement cases~ (which is what a variance is) must

have a definite program to control the emissions with

existing control technology.”

Implicit in this finding is the language used in Title VIII Sect-

ion 33 (c) (iv) of the Environmental Protection Act. The language

therein states that when the Board renders its decision in an enforce-

ment action, one of the aspects to be considered is:

“(IV) The technical practicability and economic

reasonableness of reducing or eliminating the em-

issions, discharges or deposits resulting from such

pollution source.”

Although this language is under the enforcement section of the En-

vironmental Protection Act, because a variance may be considered a

“shield from enforcement action,” it would also apply to variance de—

terminations~ The heavy weight of testimony entered has shpwn that

the technology is not presently available to abate cyanide in a re-

finery stream. In this type of instance a good faith program of con—

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tinuing research and development will be considered a viable alternate

for a firm project completion date. It is emphasized that this pro-

gram must be continuing. It is not enough to state that technology is

not available. A Petitioner must attempt to develop, within its fin-

ancial ability, a viable abatement technology. The Board feels that

Union Oil is indeed pursuing this approach.

This method of granting a variance is not without precedent. In

PCB 71-111. Sherwin Williams vs. Environmental Protection Agency, a

variance was granted requiring a continuation of study regarding mer-

cury abatement methods. The problem of cyanides in refinery streams

is not unique to the Board. In Shell Oil v. Environmental Protection

Agency, PCB 73-116, variance was denied, and in Clark Oil & Refining

v. Environmental Protection Agency, PCB 73-238, variance was granted.

The facts in both the above cases constituted the reasons for the di-

vergent Board actions.

Hardship in Event of Denial: One of the primary preconditions for

the grant of a variance is a showing of hardship if compliance is re-

quired. Union Oil Company alleges that the only alternate to variance

would be the shutdown of the refinery. In addition to the enormous

loss of revenue to Petitioner, this shutdown would necessitate the

potential layoff of 650 refinery personnel.

At a time when energy resources are in short supply, the removal

of significant quantities of petrochemical products would impose a

significant hardship on the public in general.

Two witnesses were called or: to testify as to Union Oil’s social

value in the community.

Mr.

Roy Hassert (Will County Chairman)

test-

ified (H. 18-21) that Union Oil Company is a major taxpayer to the

township (approximately 3 million dollars a year) 

He further test-

ified that DuPage Township relies on the tax money to operate the

township. Mayor Maurice Berlinsky testified (R. 41) that Union Oil

Company is a significant employer of families in the Joliet area.

Effect on Environment: The Agency has calculated that the increase

of cyanide in the Sanitary and Ship Canal would be from 0.0255 mg/l

to 0.0257 mg/l. This is an increase of .0002 ppm. Petitioner’s fig-

ures show that during the 7-day 20-year low flow of the canal the in-

crease of cyanide would be 0.0015 ppm. It is alleged that although

this amount of cyanide can be mathematically calculated, it could not

be analytically determined in a sample of canal water (R. 334). The

opinion of Dr. Gingham was elicited (H. 335) as to the effect of such

an increase on the canal. His response was that there would be none.

The Agency in its recommendation also stated that it felt no signifi-

cant harm to the canal would occur due to this increase in cyanide

concentration.

As mentioned above this Petition for variance was submitted on 

Nov-

ember 6, 1972. At that time it was suggested that (R. 7) a one—year

variance would be required to develop a solution to Petitioner’s cyan-

ide problem. The recently received (November 7, 1973) interim report

shows tha this goal has not been met. The Board in cranting a one-

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year variance from the date of its Order will in essence be allowing

two years to develop a viable program (one year for litigation and a

one-year variance). By doing so the Board must stress that every ef-

fort be made to abate this problem as soon as possible. In granting

the variance the Board will apply some of the recommendations of the

Agency. Progress reports will be required on a two-month rather than

a one-month basis. This is in the hope that a significantly more de-

tailed report can be submitted at each reporting date.

Analysis of Petitioner’s effluent data shows that with rare excep-

tions a 0.20 mg/i cyanide level can be maintained. The variance will

set this limit with provisions for brief excursions over this limit.

This Opinion constitutes the findings of fact and conclusions of

law of the Board.

ORDER

IT IS

THE

ORDER of the Pollution Control Board that Petitioner be

granted a variance

from Rules 

408 and 1002 of Chapter 3 and Rule 1.07-

10 (c) of SWB-15 until December 6, 1974, subject to the following

conditions:

1. Petitioner’s

cyanide effluent concentration shall

not exceed an

average of 

0.20 mg/i during the

period of this variance.

2. At no time shall Petitioner’s single month aver-

age be over 0.3 mg/i cyanide.

3. Petitioner shall utilize any methods it may find

useful to keep its effluent at the lowest possible

cyanide level.

4. Petitioner shall continue to diligently pursue its

program of research and development in regards to

cyanide reduction.

5. Petitioner shall submit to the Agency bi-monthly

reports. Said reports shall include as a minimum:

A) Progress on all methods being pursued by

Petitioner regarding cyanide reduction.

B) Future work anticipated on methods being

pursued by Petitioner.

C) Any and all records of cyanide concentra-

tions in Petitioner’s effluent. At least

one determination of cyanide shall be run

per week,

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What methods if any are being used to com-

ply with (3) of this Order.

6. As soon as a technologically feasible program for cyanide

reduction has been found, Petitioner shall commence on a

compliance plan to implerient this program.

IT IS SO ORDEREI).

I, Christan L. Moffett, Cnerk of the Illinois Pollution Control

Board, certify th t the above Opini n and Order was adopted by the

Board on the ~ 

day of 

_____________,

1973, by a vote of

to

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