ILLINOIS POLLUTION CONTROL BOARD

July 

25, 1974

MOBIL OIL CORPORATION

(JOLIET REFINERY)

PETITIONER

)

PCB 73—452

ENVIRONMENT2~.L

PROTECTION

AGENCY

RESPONDENT

)

OPINION 

AND ORDER

OF THE BOARD (by Mr. Marder)

This case comes to the Board on Petition of Mobil Oil Corporation,

filed October 29, 1973, for variance from Rule 408 (a) arid Rule 1002

of Chapter 3 of the Board~sRules and Regulations, until December 31,

1974.

The Agency filed its Recommendation on December 17, 1973. This

Recommendation suggested a grant subject to certain conditions,

On March 25, 1974, Mobil filed an Addendum to its Petition for Var-

iance supplying more information as to research in cyanide, and an up-

date on sampling done by Mobil.

On April 8, 1974, the Agency filed a Supplement to its Recommenda-

tion, again suggesting a grant.

No hearing was held.

The facility in question is Mobiles relatively new petroleum refin-

ery, located in Will County near Joliet on 1-55. This refinery has a

design rate of 164,000 barrels of oil per day. The products from the

refinery range the entire gamut of petroleum products, including liq-

uid petroleum gas, motor gasoline, jet fuel, diesel fuel, heating oils

and coke.

The refinery 

construction was completed

in late 1972 and was operating

design capacity in early 1973, with a full-time work force of 500

people.

Water for use 

in the facility comes from the

Des Plaines 

River, for

boiler

feed, cooling tower makeup, and non—contact cooling water. Well

water is used for general domestic type uses. Wastewater streams are

segregated in the refinery with one system for storm water runoff, one

for non—contact cooling water, and one for “oily” process water, which

is processed through on-site waste treatment facilities. This facility

was issued construction and operating permit #1971—EA-738 on September

17, 1971, by the Agency. Upon expiration of this permit, Mobil applied

—

179

Lr r~received permit #l)72-E2~l47 OP on November 1, 1972. As Mobil

did not contemplate a cyanide problem this constituent

was not present-

e.~. 

i.~ F

e

pera~ prcceeh

js

Rule 408 aj sets a limit of cyanide discharge at .025 mg/i.

It is alleged that refineries have not historically beer significant

sources of cyanide discharge.

Af.~eL startup aria initial operation at design capacity Mobil sampled

refinery effluent for cyanide concentrations. The initial sample taken

February

27, 1973, showed a 1.30 mg/I concentration, As will ne ex-

plained belo~,Mobil does not have great confidence in the results of

its sample resting, bUL does state tha~it believes with a reasonable

certainty that the effluent exceeds the .025 mg/i hint

N

bi believes 

tf at nos~ of

the cyanide 

is tormea

in the refinery

Juid tary ic

cracking 

uri~. (ICC

Cyanide formation is a funcLion

of hJgt teirparatures

ir th~FCC mechanism, and depends on the nitrogen

con mt

r tie crude st 

~e proc seed.

ti

cy&i~de

rae

tars

~he wasme water system when certa~r

pe I ~fe IC

ar~wlshe by wa~erto remove deposits of soluble sa1t~

rc~ accum i~tc i tie ~ipan

ie

estimated that 

the

cyaniae

~orffcd

1

tha refi nary c. re~ fror the FCC

The remainder is probab~

f  ci 

t cotmi 

ii.

it,

t~e pre.ert time, 80 cf tIe cyanice ~ removed from the wastewater

stream at the refinery sour water stripper.

¶ne unit was designed to

remove sulphides, phenols, and anmionia from the water and coincident-

ally i~ removes 80 of the cyanide. Mobil feels but has no test data

to show, and in fact allege~that there are no tests to show, that the

discrarge from the stripu~r is complex as opposed to simple cyanide.

IlObil treats 2.4 mcid of waste water per day This is alleged to be

considered low for a refinery the size of Mobil s, but water conserva-

tion measures are alleged to be used. With this output Mobil will be

able to discharge 

0.5

lbs/day cvan~de. Mobil further states that by

using

discharge volume 

a criteria for measuring cyanide limits, Mobil

is being discriminated against as compared to other refineries

that do

not oractice water conservati~r

This proolem is not unique to Mobil Oil~ The Agency notes that the

same type of relief has been recuested in Union Oil of California v.

PCB 72-44~

PCB 73-6’ ~

~~!ctio~nc~,

PCB 73-116; and ~

~cases

the following statementsPeP

73-238.can

be made:The

Agency notes that from tLes~

I. Recent water conservation measures by refineries

are

largely responsible for increased cyanide concentra~

tions in refinery effluenta.

1s

— 180

Cyanide in r~iinerywant water i3 io~emerab e

to traditional cyanide treatment (e g.. aJk~l ~

chlorination process) because of the prese~e

relatively stable inorganic and organic cyaiu

complexes in addition to the existence ~f ex~

ive oxidizable substances (e.g., ammoni 

~n r~

iduab organic matter not removed in secondd’~y

wastewater 

treatmer

3. Method.~ for reducing refinery cyanide problen’

are still in the research staec

There is a question as to the validity of the sampling method used

for cyanide in the sub-milligram range. When Mobil initially te~

for cyanide, tests were done in the refinery laboratory. Then 2’  ii.

sent duplicate samples for analysis by ARRO Laborator~e J et t

the Mobil Lab in ~au1sbor~, N.J an I t the anorat z~e~of td~ Il

iio~ Petroicue in

0.08,                        

+J,u 5

0.155

+0,0

0.054

0 1

+~J, E

0.099

0.200

0.144

0.04

—0 104

0.057

0.05

—0.004

0.211           

0.480       

+0 26)

0.244

0.018

Average 0.198           

0.183

Duplicative tests of other samples have shown that the reliability

of tests on refinery effluent is not high Mobil, along with the Ill-

inois Petroleum Council, is now preparing a study on testing being con-

ducted for presentation to the Illinois Environmental Protection Agenc

In the Amended Recommendation, the Agency agreed with Mobil s con-

clusion regarding the inadequacies of cyanide testing Agency investi-

gations have reached the same conclusion.

The average cyanide concentration in the refinery effluent of 3~

samples analyzed from June through September 1973 was 0.175 mg/I Pet-

itioner alleges that it can maintain a consistent concentration of 0.50

mg/I or less.

Agency effluent grab samples have shown cyanide concentrations

follows:

—

181

—4—

Date         

CN (mg/i)

12/21/72         

0.03

8/21/73          

0.18

8/29/73          

0.22

2/20/74          

0.65

Petitioner’s testing showed concentrations of cyanide as follows:

DATE

MAXIMUM

MINIMUM

AVERAGE

NO. OF

ANALYSES

Feb. 

1973

1.30

March 1973

0.78

0.15

0.47

~prii

1973

0.68

0.40

0.54

May 1973

1.77

June 

1973

0.329

O.022

0.193

July 1973

0.344

0.081

0.175

August 1973

0.337

0.040

0.140

Sept. 1973

0.480

0.018

0.253

Oct. 1973

0.690

0.018

0.311

Nov. 1973   

0.756    

0,063   

0.283      

5

Dec. 1973   

0.461    

0.261   

0.390      

4

Thru 

Jan.

II, 0.058    

0.034   

0.046      

2

1974

For last 12  1.77     

0.018   

0.258     

66

months

Mobil has and is investigating various methods to abate the cyanide

problem. These include: 1) Parson’s 

HCN

Destruction Process, 2) Pro-

con’s Removal Process, 3) Ultraviolet Radiation, 4) Powdered Activated

Carbon, and 

5) FCC Process Improvements.

Parson~s HCN Destruction

Process:

This process is described as a vapor phase hydrolysis by catalytic

action. A pilot

unit 

is being

set, 

up at Mobi1~s Torrance,

California,

refinery. 

Mobil states that experimental data shows a 

99 removal of

cyanide in coke ovens but the

life of the catalyst was relatively

short 

because tar constituents foul the catalyst pores. Mobil

has

al-

located $40,000 to carrying

out

the pilot project.

The

unit

was

have been installed in May of this year and

run

for a 3-4 month test.

Procon’s Removal Process:

No details have been worked

out in 

this case.

Procon is evaluating

a sample of Mobil’s effluent to determine if the process will be appli-

cable.

Ultraviolet Radiation:

Experimentation is being done at Mobil’s refinery laboratory to de-

termine whether this is a viable method for removing cyanide.

13

—

182

Powdered Activated Carbon:

The initial research on this method was done by the Calgon 

Corpor-

ation, using adsorption and catalytic oxidation on granular activated

carbon.

Mobil 

has experimented with the same concept using powdered carbon

in the 

refinery activated sludge system. During a four-day full-scale

test the carbon level was maintained at 400 mg/l in the second aeration

tank. For the first two days of the test cupric chloride 

was

absorbed

onto carbon for 20 minutes prior to carbon addition by 

Mobil. 

For the

last two days, cupic chloride was pumped continuously into the second

aeration basin.

Mobil feels that results from carbon-copper addition are inconclus-

ive. Though Mobil acknowledges a certain 

degree of removal, 

it is Mo-

bil’s conclusion that this amount is not adequate to meet the Rule 408

(a) required level. Mobil 

will

continue research on this method of

removal.

~ocessImrovements:

Bench scale work is being done toward lowering cyanide formation

in the

catalytic processing 

unit. It might

be possible to steam purge

the effluent to strip the catalyst of flue gas containing carbon mon-

oxide. Carbon monoxide in the presence of nitrogen promotes the dev-

elopment of cyanide. Mobil does not feel that this method will be a

solution for achieving the 0.025 mg/l required effluent concentration.

Environmental Impact:

Mobil alleges that its 

cyanide

discharge has no significant effect

~n the levels

found in the Des Plaines River. Mobil further 

alleges

bhat analysis of water samples taken above and below its effluent out”

fall to the river show no increase in cyanide levels.

Mobil has assumeci

~ flow rate

of approximately 

4.0 billion gallons per day in stating that

it

not

practical to measure

cyanide using current techniques.

The Agency has calculated that based on a 0.5 mg/l average cyanide

discharge and an average 

flow

for the Des Plaines River being 4.0 bil-

lion gallons per day, the increase of cyanide in the river would 

.0003 mg/l. At a low flow of 1.18 billion gallons per day, the increase

caused by the effluent would be .0010 mg/i.

The Board takes particular notice and expresses some concern that no

data is given for concentration at the edge of the mixing zone. This

data will be required in future proceedings.

Mobil alleges that the measured cyanide concentrations in the river

are below the 

water quality level set in Rule

203

(f) of Chapter 3 of

our

Rules and Regulations. Mobil further alleges that the cyanide dis-

charged from its refinery is a complex type cyanide which is not toxic

as is the free cyanide ion.

13—

183

boo

1

~ tt~ ~Ma

~..

~ne~tn:

~ J.ec nmemtIc~ btaUiS that it ~s

01101 t

hOt :~~‘T

cnJ

this variance would have a negligible ad—

n ~ c n’~

‘~

nnentc~. n.pact. as long as Mobil s effluent cyanide con—

~:ot~

~Io:i I. e~

too~.oeed ~~50 mg/I as a monthly average or 0,80

o~e Mobil has stated above that it can maintain

~ 50 ng/l ranged this euggestion will he incorp—

-‘

n ‘o •t~

~ c2~

I

cL Ic ~ t~o-~”oi:::,rcement ol

Rule ~08 (a) woulc& 

impose an

~~ab:L~ hardship on it in that there :Ls no aom~r—

i1~

r~thod of removing cyanide to the required level.

There—

oci ~  

t~iniL 

would have to shut down the entire refinery.

w o~d ~ cdt.

~

~ employment to 500 persons at the refin—

~ ic~c~of i5’~ui~Iion gallons of gasoline, 5.7 million

~~csoty~t   

Idel C2.9 

million gallons of heating oil, 8,3 million

:guefled petroleum

gas~. 

and 4.7 million ~ailons

resid-

io~ C,.   

per ~day period. Closure would also impose a great economic

to

C

Rccrd ~ioes not

usualiy grant variances to continue to pollute,

a date certain :Ln which the non—complying facility

Cror 

tht

into

compliance. 1isuaiiy 

this is done by setting down

o ~

schedule as a condition 

to a variance which must he ac—

coted by ‘.he Petitioner before the variance takes effect.

Here we

.L ~ve a otruation where not only are there no removal techniques that

Li

bring

Mobil into compliance, but also 

it

rs agreed by both parties

otot

r’e

ceasurement method has such a low reirability that 

~t cannot

C”- 

Cerermined with any type of certainty what 24obi1h~ exact oischar~es

i-tOe~ r o~co’is the Board will 

grant ~4obii a variance trom Ruie

-cppires to cyanide, without a fixed compliance plan.

:md ‘as granted variances such

as

this wnere ct appeared that

LI’.

~.as 

no technology to abate the violation.

The Board has condi—

I- Lo ~ed eucci variances on Petitioner~ s entrance into a research orogram

tc’cate:~v .brina the facrlity into comnliance.

Sherwin cqrli~ains

~o~e:~aiProte2~onAency,

P(B 71—Ill

Union ~~C~’~r,Environ—

:o-oci 

7~otection Acrency, PCB 72—447; Koppers Co., Inc. vo Envrronmen—

PCB 73-365, POP ‘4—63. Tfle Board snail continue

t ~ pr~cti.ne in this matter.

Mobil Oil will submit br—monthly reports

-Mw Mow cv 

as to research being done to abate the cyanide in its eff—

Cocci. a~oi OLSO

‘:0

report on any research being

tone 

in techniques for

~n orements of low levels of cyanide in refinery effluent,

CLoc Board will grant a variance for six months from the date of this

Order, which constitutes an eight—month variance from

the original I 

ii-

tug date. The reason for this

somewhat shorter grant is that the Board

finds certain allegations unproven and would desire additional proof in

future proceedings. Data as to what percentage 

of cyanide is complex

owl

Moat 

oercentage is free cyanide must 

generated, and data 

at the

~Coc of the mixing zone will also be required.

Additional information

no the status of compliance (results of research and development) as

o~ ahv’nices in, analytical

techniques wilL also be required,

—7—

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 

Mobil Oil

Corp-

oration is granted variance from Rule 488 (a) as it applies to cyanide

for six months from the entry of this Order, subject to the following

conditions:

1. Petitioner’s cyanide effluent concentration shall not

exceed a monthly average of 0.50 mg/l during the period

ot this variance.

2. At no time shall Petitioner’s effluent exceed 0.8 mg/l

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, starting in 30 days after the entry of this

Order, file with the Agency bi-monthly reports. Said re-

ports shall include, but not be limited to:

A. Progress on all methods being pursued by Petitioner

regarding cyanide reduction.

B. Future work anticipated or methods being pursued by

Petitioner.

C. Any and all records of cyanide concentration in Pet-

itioner’s effluent. At least one determination of

cyanide shall be run per week.

D. What methods 

any are being used to comply 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 implement this program.

I, Christan L~Moffett, Clerk of the Illinois Pollution Control

Board, certify 

that

the above Opinion and Order was adopted by the

Board on the 25th day of July, 1974, by a vote of 4 to 1.

Mr. Henss dissents.

13

—

185