i.

United States
Environmental

Protection

Agency

Office of Air Quality

Planning and Standards

EPA-450/3-79-008
March 1979

Research Triangle Park NC 27711

Air

bEPA

5
'--I

,~

A Review
of Standards
of Performance
for New

Stationary

Sources

Petroleum

Refineries

5
I

Il

III
I

I
L
II

I
I

C1

EPA-450/3-79-008

A Review
of Standards
of Performance
for New

Stationary

Sources

Petroleum

Refineries

by
Kris Barrett

Metrek

and

Alan

Goldfarb

Division of the MITRE Corporation

1820DolleyMadisonBoulevard
McLean, Virginia 22102

Contract

No. 68-02-2526

EPA Project
Emission

Officer:

Standards

ENVIRONMENTAL
Office

Division

for

PROTECTION

of Air, Noise,

Office of Air Quality

Bibb

and Engineering

Prepared
U.S.

Thomas

and

Planning

AGENCY

Radiation

and Standards

Research Triangle Park, North Carolina 27711

March

1979

This

report

has been

reviewed

by the Emission

Standards

and Engineering

Division, Office of Air auality Planning and Standards,

Office of Air, Noise
and Radiation, Environmental
Protection Agency, and approved for publication. Mention of company or product names does not constitute endorsement
by EPA. Copies are available free of charge to Federal employees,
current
contractors
and grantees,
and non-profit
organizations
- as supplies permit
from the Library Services Office, MD-35, Environmental
Protection Agency,
Research Triangle Park, NC 27711; or may be obtained,
for a fee, from the
National Technical Information Service,
5285 Port Royal Road, Springfield,
VA

22161.

Publication

No.

EPA-450/3-79-008

ABSTRACT

Standards

This report
Stationary

of Performance

reviews the current

J - Petroleum Refineries
Sources: Subpart

for New

it includes

standards, the status of current applicable

summary of the current

and the ability
control
technology,
test results
standards
Compliance
modifications
are made for possible
needed for
including
future studies

of refineries to meet the current

are analyzed and recommendations
and additions to the standard,
unresolved

iii

issues~

~CKNOWLEDGEMENT

The

authors

their

time

many

helpful

Lowenbach

wish

and patience
suggestions

and Ms.

Sally

to

acknowledge

those

during

the

and

technical

Price

who

preparation
assistance

gave

of

so

this
of

of The MITRE Corporation

generously

report.
Mr.

of

The

William

are

greatly

appreciated.

jj
iv

TABLE

OF

CONTENTS

Page
LIST OF ILLUSTRATIONS

vii

LIST

OF TABLES

V111

1.0

EXECUTIVE SUMMARY

1-1

1.1
1.2
1.3

Particulate
Matter
Carbon Monoxide
Sulfur
Dioxide

1-1
1-3
1-4

1.4

Hydrocarbons

1-5

2.0

INTRODUCTION

2-1

2.1

Purpose

2-1

2.2

Background Information

and Scope

2.2.1

Catalytic

2.2.2

Description

2-2

Cracking
of Fuel

Units

2-5

Gas Combustion

Device

2-9

3.0

CURRENT STANDARDS FOR PETROLEUM REFINERIES

3-1

3.1
3.2

Facilities
Pollutants

3-1
3-2

Affected
Controlled

3.2.1

Standard

for

Particulate

3.2.2
3.2.3

Standard
Standard

for
for

Carbon
Sulfur

3-2
3-2
3-3

Requirements

3-3

3.3

Monitoring

4.0

STATUS OF CONTROLTECHNOLOGY

4-1

4.1

Scope of Industrial

Operations

4-1

4.1.1

Distribution

of

Sources

4-1

4.1.2

Industry

Growth Pattern

4-1

4.2

4.3

and Reporting

Matter

Monoxide
Dioxide

Applicable
4.2.1

Fluid

4.2.2

Fuel

Achievable

Control

Technology

Catalytic
Gas

4.3.1

Fluid

4.3.2

Fuel

Catalytic
Gas

Cracker

Combustion

Emission

to Meet Standards

Device

Levels

4-7
4-21
4-23

Cracker

Combustion

4-3

Device

4-23
4-25

TABLE OF CONTENTS(Condluded)
Page

4.6 SpecialProblems
UsingControlTechnologies
4.4.1

Wet

4.4.2

Condensable

4-25
4-25
4-28

Scrubbers

Particulates

4.5 EnergyNeedsandEnvironmental
Effects

4-30
4-30

4.5.1

Erq~ander Technology

4.5.2 CarbonMnoxiie Oxidation Catalysts

4-32

4.5.3

Sulfur Dioxide Catalysts

4-33

5.0

INDICATIONS
FROM
TESTRESULTS

5.1

Test

5.2 Analysis of Test Besults

5-5

6.0

ANALPSIS
OF POSSIBLEREVISIONS
TO THESTANDARD

6-1

Coverage

6.1: Particulate

5-1
5-1

in R~gions

Matter

6-1

6.2

Carbon ~ianoldde

6-4

6.3

Sulfur Dioxide

6-5

6.4

Hydrocarbons

7.0-

CONl=LUSIONS

7.1. ParticuZate
7.2

Carbon

6-7
7-1

Matter

7-1
7-1

Monoxide

7. 3 Sulfur Dioldde
7.4

Hydrocarbons

8.0

RECOMMENDATIONS

8.1
8.2

Particulate
Matter
Carbon
Monolcide

8.3

Sulfur Dioxide

8.4

Hydrocarbons

9.0

REFERENCES

APPENDIXA

7-1
7-2

8-1
8-1

8-1

8-1
8-2

9-1

REPORTEDFCC UNITS AT.PETROLEUMREFINERIES

vi

A-i

LIST OF ILLUSTRATIONS
Page

Figure Number

2-1

Processing Plan for CompleteModern

2-3

Refinery

2-2

ModernFluid Catalytic CrackingUnit with

Controls

4-1

and Energy

Recovery

Effect of Particle Size on Collection

Efficiencyof an Electrostatic Precipitator

vii

2-8

4-9

LIST

Table

OF TABLES

Number
2-1

Page
Potential
Within

2-2

Sources

Nationwide

4-3

4-4
4-5

Bed Catalytic

Emissions,

Geoeraphic
Cracker

4-2

Emissions
2-6

Fluidized

Regenerator
4-1

of Atmospheric

Refineries

Cracker

Uncontrolled

Distribution

of Fluid

2-10
Catalytic

Units

4-2

~ Reported
Predictions
1977 - 1980

of Refinery

4-4

approximate

Characteristics

Collectir~

Eql~~nn~ent

Particle

Collection

Effects

of

Growth

of Dust

and

Mist

4-15

Efficiency

Variables

on

Dust

4-16
Collection

Equipment

4-18

4-6

Use of

4-7

Conrpliance

Test

Data for Particulate

4-8

Compliance

Test

Data for Carbon Monoldde

4-26

4-9

Compliance

Test

Data for Sulfur

4-27

4-10

Carbon

Condensable

Monoxdde

Oxidation

Particulates

from

Catalyst

Matter

Dioxide
FCC

4-29

NSPS Compliance

Test

Data

- Petroleum

Refineries

5-2

Geographic
Affected

6-1

Bazardous

4-24

Unit

Regenerators
5-1

4-20

5-2

Distribution

of Possible

NSPS'

Facilities

5-3

Hydrocarbons

Unit Regenerators

Emitted

from

FCC

6-8

viii

1.0 EXECUTIVE
SUMMARP
New Source Performance Standards

(NSPS) for petroleum refineries

were promulgatedby the EnvironmentalProtection Agency(EPA)on

March 8, 1974. These standards regulate the emission of particulate
matter and carbon monoxide, and the opacity of flue gases from fluid
catalytic

cracking (FCC) unit catalyst

regenerators

regenerator incinerator-waste heat boilers.

emission

of sulfur

dioxide

and FCCunit

They also regulate the

from fuel gas combustion devices.

These

regulations apply to any affected facility which commenced

construction

or modification

after

June 11, 1973.

The objective of this report is to review the NewSource Performance Standard

(NSPS) for petroleum

refineries

in terms of the impact

of new developments in control technology, industry operating condi(

tions,

process changes, and other issues that have evolved since the

standards

were promulgated.

based on NSPS compliance test

Possible

revisions

results,

are also analyzed.

following paragraphs summarize the results

analysis,
1.1

Matter

The current

NSPS for particulate

on electrostatic

precipitator

matter

technology.

j~his report reflects

demonstrated

control

action.*

emissions were based

The use of multi-stage

cyclones in conjunction with an electrostatic

the best

precipitator

technology.

information and data available

1-1

The

and conclusions of the

as well as recommendations for future

Particulate

considered

to the standard,

is still

A number of

in June 1978.

refineries
matter
is

are using
loading

prior

then followed

can also

high-efficiency
to energy

recovery

by a precipitator.

be used

this

task.

The three

0.76

to 1.35 kg particulate

in an expander

regenerator

test

runs

had

exhaust

a range

gas

This
scrubbers

stream.

of emission

coke burn-off

data from tests

no change to the present

turbine.

for analysis

(NSPS ~ 1.0 kg/kg).

and previous

particulate

and venturi

was available

matter/kg

coke burn-off

compliance test
standard,

test

to reduce

Bag filters

on a PCC unit

Only one NSPS compliance

of 1.01 kg/kg

separators

during

values

with

from

an average

Based on this

one

performed to support the

particulate

matter

standard

is

recommended.

and
late

Technological

advances

catalyst-to-feed

ratios

matter

based

mass

on coke

burn-off

late

also

matter

increase

had

rates.

in

the

emitted
of

Technological

the

the

effect

regenerator,

per

hour.

the

emission

the

allowable

not

mass

emissions

This

has

of

third-stage

cyclones

or separatora.

separator

may control

the effect

of increased

to

erosion

of the

to

control

turbine

regenerator
blade

erosion

internal
is

1-2

the

rate.

is

Therefore,

coke

Lg of pa~ticuindustry

to

catalyst.

to new, high-

Use of a third-stage
emissions

cyclones.
mandatory

emission

in total

are limited

efficiency

ptlrticu-

m~d therefore

required

entrained

in controls

of regeneration

of reducing

coke formation

allowable

advances

temperature

However,

which reduce

reduce

control

catalysts,

have

emission

the new technologies

burn-off,

in

with

time due

Use of a separator
if

energy

recovery

from

an expanderturbine is incorporatedin the FCCunit regeneratorflue

gas

stream.

The available

compliance test report included an appendix

describing a problem with EPAReference Method 5 for measuring

particulate matter due to condensablesulfates Becausethis method

is the key to defining particulate matter and it determines the

compliance/noncompliance
of an affected facility, it is recommended
that Reference Method 5, as it applies
emissions,

be

to catalyst

regenerator

reevaluated.

An additional

recommendation

for

the particulate

matter

stan-

dard is to require that the opacity be measured at the same time

the mass emission is measured.
needed data and will
with

the

mass

1.2

Carbon

This requirement will provide much

ensure that the opacity

emission

standard

is consistent

limit.

Mo~ri~

The best demonstrated

control

technology

for carbon monoxide

(CO)is considered to be the carbon monoxideincineratorraste

boiler.

No compliance test data were available

emissions

from FCC unit

monoxide boilers.
of reducing
standard

regenerators

other than carbon

waste heat boilers

are capable

the emission of CO to 0 to 14 ppm, far below the current

of 500 ppm.

The standard

was established

permit control of COemissions by regenerator

There

for carbon monoxide

using controls

These incinerator

heat

is no data

to substantiate

the level

1-3

at 500 ppm to

in-situ

oxidation.

of CO emissions

from

regenerators using in-situ oxidation other than journal statements of

"less

than 500 ppm."

Approximately

20 percent

of the U.S. regener-

ators are operating with COoxidation promoters (Wallendorf, 1978).

It

is reconrmended that

data

be collected

to ascertain

of these systems to reduce CO and the level

then

reevaluate

1.3

Sulfur

Dioxide

Sulfur

dioxide

controlled

the

CO standard

emissions

based

of reduction

on this

from fuel

possible,

new data.

gas combustion

by reducin.g the hydrogen sulfide

or by flue gas desulfmization

the capabiliy

content

devices

can be

of the fuel gas

(FC;D). The standard

was written

to

limit the H2S content of fuel gas, although the owner/operator has
the option of using FC;D. Ilhe available
that:

(1) all

MSPS affected

facilities

compliance test
identified

data indicate

chose to limit

the

82S content of fuel gas instead of using FGD, and (2) the technology for reducing H2S concentrations
NSPS limit

is being

increased

sulfur

content

This relationship
whether

the

content

of

fuel

original

to show the effect

expected

with

increased

before a decision

can be changed

the

to reduce

of the
imports.

is made on

allowable

h2S

gas.

so that

excluded

rationale

is no data

of feedstocEc

recommendation
device

is no longer

There

below the present

should be considered

standard

Another
combustion

used.

substantially

for

is to change
a regenerator

from compliance
excluding

the definition

of a fuel

Fncinerator-waste

heat

with

the boiler

1-4

the SO, standard.

from the standard,

gas

boiler
The
even

when using fuel gas as an auxiliary fuel, is not known. A third

recommendation concerns the monitoring of hydrogen sulfide in fuel

gas. The lack of a continuousmonitoringmethodfor H2Shas been

reported by EPARegional personnel as a weaknessin the current NSPS
(Watson et al.,

1978).

There is currently

no NSPS for sulfur

the FCCunit regenerator/regenerator

Arthur D. Little,

Inc.

dioxide

emissions

incinerator-waste

(1976) has estimated

from

heat boiler.

that a SO, flue gas

control level of 300 ppm or 500 ppm will reduce emissions by 85,000
tons/year and 49,000 tons/year respectively
reduction

from their

estimate

by 1985. This is a

of 480,000 tons/year

of SO, emitted

by FCCunits in 1985. It is recommendedthat further analysis be

done to determine

this

standard

regenerator
or

solid

1.4

if

a suitable

include

an additional

incinerator-waste

fossil

standard

dioxide

allowance for

liquid

fuels.

Hydrocarbons

from uncontrolled

Radian Corporation
released

under

differing

the emission

CO boiler

FCC unit

of concern to public health

regenerators

(Bombaugh et al.,

have not been determined.

that

sulfur

and that

heat boilers using auxiliary

The emission of hydrocarbons

cials

can be developed

operating
Arthur

of hydrocarbons

or high temperature

has been established

1976).

The actual

conditions

or control

D. Little,

Inc.

is negligible

regeneration

1-5

offiby

emissions
equipment

(1976) has stated

when using

either

(HTR). New CO oxidation

promoters can reduce the temperature at which effective EITBcan be

carried
tions

out and the emissions

are unknown.

ascertain

It

from a regenerator

is recommended that

data

the need for a NSPS for hydrocarbon

1-6

under

these

be collected
emissions.

condito

2.0

INTRODUCTION

2.1

Purpose

and Scope

On March 8, 1974, the Environmental Protection Agency promulgated

NewSource Performance Standards (NSPS)for Petroleum Refineries (39

FR 9315).

Revisions were made on October 6, 1975 (40 FR 46250) and

again on July 25, 1977 (42 FR 37937). These standards establish

emissions limits and require emission testing;

monitoring; and

reportingfor particulate matter, opacity,andcarbonmonoxide

from
fluid catalytic
fuel

gas

cracking unit regenerstors,

and sulfur dioxide from

combustion~devices.

The Clean Air Act Amendments of 1977 require

trator

of the EPA review,

standards

of performance

and if appropriate,
for new stationary

four years (Section Ill(b)(l)(B)).

the current

standards,

the

technology, and the ability

rent standards.

form the basis

status

of current

they are sufficient,

sources

established
at least

applicable

of petroleum refineries

and discussions

for analyses

revise

the Adminis-

every

This report includes reviews of

The compliance test

from the literature,

that

results,

too stringent,

to meet the cur-

information

with industry

of the current

control

standards

or not stringent

retrieved

representatives

to determine

if

enough. The

problems associated with the monitoring requirements of the standards

were analyzed,

and recommendations are made concerning

changes or studies to be conducted.

2-1

specific

Also discussed are problems at

petroleum
refineries that relate directly to the environmental
pollution load emittedand that mayaffect present or future NSPS.
2.2

BackRround information

A petroleum refinery
useful products.

transforms crude oil into a variety of

The petroleum refining industry produces more than

2500 products that can be categorized into the following classes:

fuel gas, gasoline, kerosine,

fuel oil, lubricating

oil,

grease, wax,

asphalt, coke, chemicals, and solvents. There is no "typical"

refinery,

since the number of products and the product mix varies

widely within a refinery

as well as between refineries.

The manu-

facturing processes also vary depending on refinery age, type of

technology, capacity,

location,

Petroleum refinery

and type of crude processed.

operations

involve physical

separation

componentsof the crude oil (e.g., crude distillation)

conversion
ents

processes

of the oil

into

molecular weight oils

which transform
more useful

and chemical

some of the less useful

products

(e.g.,

of

cracking

compon-

of high

into lower molecular weight products

such as

gasoline).

The processing
in Figure 2-1.
distillation
mediate,

sequence of a modern refinery

The crude oil

tower where it
and heavy fractions.

to a vacuum

distillation

from the vacuum still

unit

is illustrated

is heated and charged to an atmospheric

is separated

into

The bottoms
for

further

are thermally

cracked

2-2

several

light,

inter-

from the tower are sent

separation.

in a coker

The bottoms

to produce

DRY GAS

WET GAS

~-1
GAS

PIANTS

LIGHT

I~

LP GAS
I

~ rPOLY

IYI'1

PLANT

SATURATE
AND

NAPHTHA

UNSATURATE

t:
MOTOR

POLY GASOLINE
ALKYLATION

- FITEL GAS

ALKYLATE

GASOLINE

STR~IMr
RUW
GbSOLIWE
LICRPHyDROCRACKEDGASOI~~__I
~

HUW

CA~*L~~ICHZS

NAPTHA

REWRMMG
UNIT

e~

AVIATION

GASOLINE

:o

REFORMATE

vl
5

AYDROGW

v,

h)

LIC~

UNIT

DISTILLATES I

HYDRO

KEROSENE

HYDROGEN
TREATING

MIDDLE

HEAVY GAS on.

I T

_I

CAS

OIL

CRACKING
UNIT
I
' I
-I
CATALYTIC

L~C

I,

Puar

GASOLINE
TREATER

SULNR

CATALYTIC
) I

GASOLINE
LICAI FUEL OIL

DIESEL
FUEL

SULPIIR

I HYDROGEN SITLPIDE

CRACKING

I HYDROGEN)
PLANT

GASOLINE

CRACI(ED
CAS

NEL

OIL

HEAVY

VAC.

TO

CHEMICAL

KEROSENE

CRUDE
OIL

OLEFINS

RAW

LURES
WAXES

~CRPAses

UNIT

REDUCED
CRUDE

OIL

I c~uos
O~L

COKER GASOLINE

LURE
LUBE

ASPHALT

RESIDUUM

ASPHALT

COKER
1

-COKE

Source:

HEAVY FVEL

OIL

STILI.

I SEPARATION
I

PROCESSING

DISTILLATES

Lestet.1973.
FIGURE

2-1

PROCESSINGPLANFORCOMPLE'TE
MODERNREFINERY

wet 8881 coker gasoline, and coke. B portion of the bottoms from the
,,,,U,.till

may be processed

atmospheric
the

catalytic

the

gas

these

distillation

cracking

oils

units

nrnaber
for

and vacuum

to
is

and then

to a catalytic
with

used

as feedstocks

These

fuel.

reformer

from the

refinery

the

distillation,

convert

The gasoline
to improve

other

~mits

streams

for

from

the

octane

to make gasolines

marketing.

The vet
Mits

streams

from

and -fractionated

gas,

and unsaturated

and saturated

light

hydrocarbons

gas

are

gas

combined

is

used

saturated

are

as fuel

unsaturated
are

the

crudes

refinery

ate

blended

cracking

into

unit
heavy

vacuum

gas

can be processed
Only a few process

atmosphere--the

catalytic

into
units

oils

atoms.

cracking

unit,

2-4

chain,

The fuel
chain

primarily

isobutane,

Mit

the

to form isoparaffins
the

unit,

diesel

oils,

emit pollutants

straight

alkylation

and reduced

lubricating

petroleum

The unsaturated

isobutane

into

cracking

The straight

the

from the crude

blended

and

gasoline.

increase

and

liquified

chain

5 carbon

in

to

are

gas,

hydrocarbons,

with

gasoline

distillates

3 to

into

unit.

react

fuel

furnaces.

in an alkylation

blended

oil.

from

the

hydrocarbons

coker,

branched

chain

The middle

furnace

in

into

and the branched

processed

which

containing

hydrocarbons

hydrocarbons

and

are
units.

and distillate

blended

Gas oils

units

and hydrocracking

gasoline
fed

into asphalt.

octane.

the coker

and Set
crude

wares,
directly

the coker,

fuels
oil

rmit,
and
from

some

and grease.
to the
and the process

heaters.

Pump seals,

operations
that

valves,

are sources

may be released

of the

sources
2.2.1

barrels

processes

Cracking

cracking

yield

Three

the

fixed

bed

(Houdry

and

the

fluidized

bed.

The fixed
refineries
phased

still
out

There
operating
oil

are

combined
per

capacity,

the

During
crackers
capacity
day.
since

is

process.

are

scheduled

some units

units

4.7

to be placed

figure

may replace

2-5

(Thermofor

not

process),

and only
bed process

three
is

units

being

million

currently
barrels

16 fluid

321,000

represent

existing

older

of

bed

in operation.

approximately
does

of

have been used:

cracking

an additional

is

because

method.

of processing
2 years

in the

catalytic

cracking

obsolete,

catalytic

but

processes
bed

this

units

from the catalytic

The moving
use

bed

next

this

moving

considered

the

However,

cracking

thermal

cracking
the

into

Almost 5 million

of the product

capability

of these

2-1.

heavy oils

thermally,

replaced

16 refineries

122 fluidized

with

daily.

catalytic

oil

and only

this

converting

was accomplished

process),

use

and some

in Table

in catalytic

of catalytic

bed process

summarized

products.

completely

types

Air pollutants

from a refinery,

for

daily

and quality

process.

and sampling

Units

and lighter

have almost

the improved

are

is a process

are processed

Originally,

emissions.

emissions,

gasoline

leaks,

the environment

cracking

of oil

U.S.

into

Catalytic

more valuable

vents,

of fugitive

of these

Catalytic

relief

The
barrels

increased
units.

Also,

of

TBBLE

2-1

H)TEHTLBL
SOURCES
OFATMOSPBWIC
~IISSIOHS
WITHZN
gEpINERZES
Source

Type of Emission

Particulates

Sulfur

Catalytic Cracker,Fluid Coking,

Catalyst
Heaters,

Oxides

~itrogen

Regeneration, Process
Boilers, Decoking Opera-

tions,

Lncinerators

Sulfur

Recovery

Unit,

Catalytic

Cracking, Process Heaters, Boilers,

DecokFng Operations, Unit Begenetations, Treating Units, Flares
Process Heaters,
Boilers,
Regeneration,
Flares

Oxides

Catalyst

Storage Tanks, Loading Operations,

Bydrocarbons

Vater Treating. Catalyst Begeaeration,

cess

Barometric
Beaters,

Condensers,

Boilers,

Pro-

Pumps~

Valves, Blind Changing, Cooling

Towers,

Vacuum Jets

Carbon~bnoxide

Catalyst E~egeneration,
Decoking,

Odors

TreatingUnits, Drains, TankVents,

Compressor- Engines,

Barometric Condensers,

Water

Source:

Diclrcer~Qan,et al.,

Incinerators

1977,

2-6

Separators

Sumps, Oil-

although
some
unitsrepresent
additionsto refinerycapacity,this
figurerepresents
the total capacity
of therefineryafter the
addition

Thefluidized catalytic cracking(FCC)process uses a catalyst

in the formof fine particlesthat are fluidizedwitha vapor. The

fluidized catalyst is continuously
circulatedbetweena reactionzone

anda regeneration
zone. Twotypesof FCC
units are commonly
used
In

the

"side-by-side"tYPe,the reactionandregenerationchambers

are separatevesselsnextto eachother. In the stackedtype,the

reactor is mounted
on top of the regeneratorandthe twovessels

appearas onewhen
viewed
externallyOthervariationsin FCC
design
andoperationrelate to the typeof catalystemployed
andthe design
of the catalyst transfer line betweenthe regeneratorand the reactor~
However,the operating principles of the various FCCreactors are
essentially

the

same.

A schematic diagramof a fluid catalytic cracking unit is

shownin Figure 2-2. In operation, the gas oil is fed to the bottom

of the riser pipewhereit joins the hot, regeneratedcatalyst. The

fuel is vaporizedandflowsupward
alongwith the catalyst particles
Thecrackingreactiontakesplace in the riser. Because
the reaction
is endothermic,coolingof the reacting mixtureoccursas it rises
into the reactor Theproductgases exit throughthe top of the

separatorandthe catalystparticlesdropinto the strippersection

where they are blownwith steam to strip hydrocarbonsthat are
2-7

CARBCe~

PBODUCT

'STEAn

MNOXIDE

ELECOROSTATIC

BOILER_L_
AUX. mTEt -~

I
I

IpRECIPfTATOR
I
TO
STAGE

WATER

DUST

REACTOR

STEAn

POWER

ArR

ST~A~

ENERGY
EKPAHDER
SEPARATOR
h,

do

II

\STEAH
TURBINE

WOTOR
GENERATOR

111

BLOWER
DUST

REGENERATOR

AIB
REGENERATED

GhS

GATAtPST

OIL
FEED

FIGURE

AIR

2-2

MODERNrLUIOCATALITIC
CRACKINGVNIT
WI'THCONfROLSANDENERGYRECOVERY

EXRAUST

entrained on the catalyst.

During the cracking process, the catalyst

loses its activity due to the formation of coke deposits. In order

to restore the catalytic activity,

the spent catalyst is passed into

a regenerator where the coke is burned off in a controlled combustion

processwith preheatedair. Thehot regeneratedcatalyst then flows

to the bottom of the riser to mix with incoming gas oil feed and the
cycle

is repeated.

Theproductsof combustion
are vented throughthe top of the
regenerator.

The regenerator Vent gases contain particulate matter

from entrained catalyst, sulfur oxides from sulfur retained in the

coke, carbon monoxidefrom incomplete combustionof coke, hydrocarbons,

nitrogen oxides, aldehydes, and ammonia.Table 2-2 lists emission

factors for each of these pollutants

discharged from an uncontrolled

fluid bed catalyst regenerator along with the potential nationwide

emissions based on the current capacity of fluidized
reactors

in

the

bed catalytic

U.S.

2. 2. 2 Description of Fuel Gas Combustion Device

Fuel gas is produced in a refinery from a wide variety of pro-

cess operations including: crude oil separation, catalytic cracking,

hydrocracking, coking, and reforming. The gas is treated and then
used in process heaters, boilers, flares, and various other places in
the refinery.

A fuel gas combustion device is quite literally

any

equipment in a petroleum refinery that is used to burn fuel gas.

Fluid coking units,

fluid catalytic
2-9

cracking unit incinerator-waste

TABLE

2-2

NATIONWIDE
PLUIDIZED
BEDCATALYTIC
CRACKER
REGENERATOR
EMISSIONS,
UNCONTROLLED
Estimated

Pollutant

Partieulacea
Sulfur
Oxides
Carbon Monoxides

Hpdrocarbons

Emission Factor

(kg/m3
freshfuel)a

0.267
- 0.976
0.898
-1M5
39. 2

0. 630

Maximum

DailyEmission
(kg)b

2.1x 105_ 7.7n 105

7.1x iOS
-12 x 10~

Annual

Emission
(kg)b

6.9x 107- 2.5x LOB

23x 108- 3.9x 108

1.0 x 1010

1.6 x 108

3. 1 x 10

5. 0x10

Estimated

nirroge~
Orides 0.10)
- 0.416 8.4x104
- 3.3x105

2.8x 107
- 11x 108

Aldehydes

0.054

4
4.3 x 10

1.4 x 107

Ammonia

0. 155

1.2 x 10

4.0 x 107

aU,S, EPA, 1973.

bCalculated from capacitp data reported in Cantrell, 1978.

heat boilers, andfacilities that burnfuel gas to producesulfur or

sulfuric acid are excludedfromthe NSPS
definitionof a fuel gas
combustion
device. Fluegasesfromthese sourcesare ventedto the
atmosphere
with or withoutheat recoveryand/or treatment

2-11

3.0 CURRENT
STANDARDS
FORpETROLEUM
REFZNERIES
3.1

Facilities

Affected

TheNSPS
for petroleum
refineriesareapplicable
to fluidcatalytic cracking unit catalyst regenerators,

fluid

catalytic

cracking

unit regenerator
incinerator-waste
heatboilers,andfuelgascombustiondevicesthat commenced
construction
or modification
after
June

11,

1973.

Thefollowing
termsarepertinentto the determination'of
the
applicabilitY of the NSPSto a facility
A petroleum

refinery

is any

facility
engaged in producing
fuel oils, residual fuel oils,

gasoline, kerosene, distillate

lubricants, or other prodgcts through
leum

redistillation,

or through

unfinished

petroleum

Construction

of petro'

derivatives

the fabrication, etection, or installation

is

of an affected

distillation

cracking or reformingof

.. any apparatus to whicha standard

facility,

construction
that is completed
This includes
well
as
the
more
commonsituation
within
an organization
as
designed
and
constructed
by 8
in which the facility
is

is applicable
contracto~.

A modification

any physical changein, or changein the

~s

of~ ~

existing facility
which increases
(to
which
a
standard
applies)
the amount of any air pollutant
that
facility
or
which
results
emitted into the atmosphere bS'

method of operation
in the

emission

of

any air pollutant (to whicha standard

applies) not pfeviously emitted into the atmosphere However,

rates up to design capacity, relocaincreases
in production
and fuel
tion or change in ownership of an existing facility,
switches
if
modate such

designed to accomthe equipment

was originally
considered
to
be
modifications.
fuels,
are not

Reconstruction
to

such

an

is greater

is
extent

the

of components of
replacement

a facility

that the capital coats of the new components

than 50 percent

of the capital

costs

of a compara-

After replacement, the facility

ble entirely
new facility
andeconomicallY cap8ble of complying
must be technologically
with

the

designated
the rate

NSPS.

If a facility meets these criteria,

it is

affected facility, regardless of any changesin

an
of emissions

3-1

3.2

Pollutants

Controlled

TheNSPSfor petroleumrefineries regulate the emission of:

particulate

matter

from FCC unit

catalyst

regenerators

or FCC

unit regenerator incinerator-waste heat boilers,

carbonmonoxidefromFCCunit catalyst regenerators, and

sulfur dioxide from fuel gas combustion devices,

3. 2. 1

Standard

for Particulate

Matter

Thestandardfor particulate matter has been set at 1.0 kg/1,000

kg (1.0 lb/1,000 Ib) of cokeburn-off in the catalyst regenerator
Ln.addition, no gases are to be emitted that exhibit greater than

30 percentopacityexceptfor onesix-minuteaverageopacityreading
in an~ one-hour

period.

in those instances in which auxiliary liquid or solid fossil

fuels are burned in the IrCCunit regenerator incineratorraste heat

boiler, the incremental rate of particulate matter emissionsmay
exceed the above, but not exceed0.18 g/million cal (0.10 Ib/million
Btu) of beat input attributable to the auxiliary liquid or solid
fuel.

3. 2. 2

Standard

The standard

for Carbon Monoxide

for carbon monoxide restricts

emissions

to no

greater than 0.050 percent by volumeof carbon monoxidein gases

discharged

from a FCC unit

catalyst

regenerator

3-2

3.2.3

Standard

f or Su If ur Dioxide

Thestandardfor sulfur dioxideappliesto anyfuel gas com-

bustiondevice.Thesedevicesare definedas anyequipment

usedto
burnfuel gas, suchas processheaters,boilers, andflares

Fluidcoking
units,FCC
unit incinerator-waste
heatboilers,and
facilities

sulfuric

in which

gases

are

burned to produce either

sulfur

or

acid are not included

Thestandard
prohibitsthe burningof fuel gascontaining'
in

excessof 230mg.
H2S/dscm
(0.10gr/dscf)in anyfuel gascombustion
device,exceptas discussedbelow.Thecombustion
of processupset
gas in a flare,

and process gas or

fuel gas released to a flare from

relief valve leakageis exemptfromthis standard

Thealternative to the 230mgH2S/dscm

fuel gas standardis

that anowner
or operatormayelectto treat the gasesresultingfrom
the combustion

of fuel

gas so as

t, limit the release of S02 to the

atmosphere
TheEPA
Administrator
mustbe satisfiedthat treating
of the combustion
gasescontrolsS02emissionsas effectivelyas
compliancewith the H2Sstanda~d.
3.3 Monitoring and Reporting Requirements

Continuous
monitoring16requiredfor opacity,carbonmonoxide,
andsulfur dioxide, Theregulationsre9uireownersor operatorsto

install, calibrate,maintain,andoperatea continuous

monitoring
systemfor the opacityof emissions
fromFCC
unit catalystregener-

.tors. Theopacitymonitoring
system
is to be spanned
at 60, 70,or
80 percent

opacity
3-3

The continuousmonitoringof carbon monoxideemissions fromFCC

unit catalyst regenerators vL11be required on all NSPSaffected
facilities as soon as instrument specifications are promulgatedby
EPB. This vill require a retrofit of instruments on affected facilities

already

in place.

A continuous

monitoring

system is required

for the measurement

of sulfur dioxide~in the gases discharged to the atmosphere from the

combustion of fuel gases.

Calibration

checks are made using S02 as

the calibration gas. The span is set at 100ppm BeferenceMethod6

is used for conducting monitoring system performance evaluations.
This continuous monitoring system is not required where a continuous

monitoringsystemfor the measurementof hydrogensulfide is installed.

The EPAhas not yet developed performance specifications
sulfide continous monitoring systems.

for hydrogen

Therefore, oMers and operators

electing to monitor HpSare effectively exempt from the SOpmonitoring

requirements (40 FI~46250)until EPAestablishes instrument performance specifications

for

an HZS monitor.

The average cake burn-off rate (thousands of kilograms/hour)

and hours of operation

for any FCC unit

required to be recorded daily.

catalyst

regenerator

are

Computationof the coke burn-off

rate is done using the formula in 40 CFR60.106(4).

OMers and operators of FCCunit catalyst

regenerators who use

an incineratorraste heat boiler to burn the regenerator exhaust

gases are required to record the daily rate of combustionof liquid
3-4

or solid fossil fuels (liters/hour or kilograms/hour)

andthe hours

of operationduringwhichthesefuels are burnedin the boiler

Thereportsrequiredfor NSPS
affectedfacilities are submitted
to the EPAAdministratorfor every calendarquarter within 30 days
i

of the

end of the

quarter

Thefollowingreports of excess emissionsare required:

- all one-hour periods that contain two or more six-

opacity

minute

during which the average opacity exceeds 30

measured by the continuousmonitoringsystem, and

periods

percent

as

sulfur dioxide - any Six-hour period during whichthe average

(arithmetic
average of six contiguous one-hour periods)
emissions
of S02 exceed the standard as measured by the
continuous

monitoring

system.

3-5

4.0

STATUS
OF CONTROL
TECHNOLOGY

4.1 Scope of industrial Operations

4.1.1

Distribution

of Sources

Thereare 285operatingpetroleumrefineries in the U.S.with a

total capacityof nearly18millionbarrelsof crudeoil per stream

day The largest numberof refineries are

located

in EPA Region VI

(37percentof totalrefineries
and45percent
of total capacity)
Texas,California,andLouisiana
are the threelargestrefinery
states

with 19, 14, and 8 percent

of the refineries

and 27, 14, and

12 percent of the capacity, respectively

Thefluid catalytic crackeris an essential part of the modern

refinery Nearlyone-halfof all refinerieshaveFCC

units as part

of their process.Table4-1shows
the distribution
of thesefluid
catalyticcrackingunitsbyEPA
RegionEPA
Regions
VandVIcon-

tain 53percentof theFCC

equipped
refineriesand62percentof the
refineryFCC
unit capacityTexas,Louisiana,
andCalifornia
are the
states withthe largest FCC
unit capacity(Cantrell,1978).
4.1.2

IndustN

Growth Pattern

Thegrowth
of thepetroleum
refineryindustryhasbeenaffected

bygovernment
regulation
of fuelpricesandtheoil embargo.
According
to datapresentedin the Oil andGasJournal(Cantrell,1978),27new
refineries havebeenbuilt between1975and1978. Thirteenof these
refineries werebuilt in EPA
RegionVI. Although
the actual number
of newFCCunits built in the sameperiod is unknown,
capacitywas
4-1

TABLE 4-1

GP~OGRAPBIC
DISTRIBUTION
OFFLUID
CATALYTIC
CRACKER
UNITS
Fluid
Number

Number of

Region

Refineries

1978

75-78

II
III
IV
V

7
16
20
36

(l)b
5

VI

100

13

1978

3
3
19

197
309
120
771

45

2081 147

16
15
13
2

Total

285

26

122

1975; 1978.

a Capacity in 103 barrels per stream day.

b Reduction

in number of refineries

Capacity"

1978

3
5
1

or capacity

Units

Percent

With FCCU

13
35
44
13
Cantrell,

Cracker

of

Refineries

VII
VIII
IX
X
Sources:

Catalytic

75-78

10
15
86

373 (10~b
175
5
509 111
66
3
4600

368

of

Total

Number Capacity

2
5
2
16

37
13

12
11
2
100

4
7
3
17

45
8

4
11
r
100

increased by 368,000 barrels per stream day. A distribution of this

growth in FCCunit capacity is shownin Table 4-1,
The data

from the Oil andCas

Journal

(Cantrell,

1978) on

increased capacity of FCCunits show that 50 refineries have built

new FCCunits or expanded FCCunit capacity during the period 19751978.

It is not within

the scope of this

report

to make a deter-

mination on how many of these units are affected facilities

and sub-

ject to the NSPS. During interviews with each EPARegional office,

only two FCCunits were reported as subject to NSPS. (Data from EPA
Region IX were not received.)

In Table 4-2, data from Hydrocarbon Processing

(1978) are pre-

sented to show a planned growth in.seventeen FCCunits during the

period 1978-1980. Of these, six projects are under construction and

eleven are in an engineering
struction

are

indicated

as

phase.
new

Four of the units under con-

units,

4.2 Applicable Control Technology To Meet Standards

The NSPS are based on best demonstrated
is reasonable

from an economic viewpoint.

of available

important.

control

technologies

For this

used by petroleum

technology which
reason,

a review

refineries

is very

In this section, the control technologies currently used

to meet the NSPS are reviewed,

order

control

of their

prevalence

The technologies

in the industry.

4-3

are discussed

in the

TABLE4-2
REPORTED
PREDICTIONSOF REFLNWPGROWTH
1977-1980"

CO

~11

eP*B~B~e
~E~E~E
Region

C-

Connecticut

None

indicated

Maine

_f~

Massachusetts
New Bampshire

i!

Rhode Island
Vermont

Region

II

NewJersey

Mobil, Paulsboro

New Pork

None

indicated

Delaware

None

indicated

Maryland

Crown Central,

Region

30 W/d,U80

III

Baltimore

200 Mb/d,E

Stewart, Piney

100Mb/d,P

Point

Pennsylvania

Sun, Marcus Book

Virginia

Bampton Roads

West

Energy,
Portsmouth
None indicated

Region

Virginia

Re,E
184. 1 Mb/d,
E80

IV

Blabarea

None

indicated

Florida

Georgia
Kentucky
~L~seiesippi
North
Carolina
South

Carolina

Tennessee

Phase:

Delta,

25 Hb/d,E79

CCompleted since 9/1/77, ~EPEngineering, PPPlanning, ReLReVBmPI

Udlnder

Pear:

Memphis

(77,

78,

construction

79,

80)

a Compiled as of 1/1/78 and reported in thousand barrels/day

Source:
grdrocarbon
Processing,
1978.

4-4

(Mb/d)

TAHI.E

4-2

(Continued)

R~POKT~:I) PREI)ICTIONS OP RISFTNISHYCROWTI~1977-1980"

CO

ISPAKeRion
Region

Company/C1ty

FCC

Roller

Hc~~ncry

Illfnois

None

indiana

Energy Coop,
East Chicago

indicated

Iowa

None

Michigan

Total
Alma

MLnnesota

None

ExpnnHion,E

indicated

Petroleum,
By 4 Mb/d,C77
indicated

Wisconsin

Kcfiion

VI

Arkansas
Louisiana

None indicated
Continental,

Lake

Charles
Good Hope, Good Hope
Gulf,
All.iance

30.8 Mb/d,E79
Ex 55 Mb/d,U
By 11 Mb/d,E79

Marathon,

75 Mb/d,E79

Murphy,

Garyville
Meraux

Exp.,E79

25 Mb/d,E79

Sliepherd, JenninRs
T&.S, Mermentau
New Mexico

Plateau,

Oklahoma

Continental,
City

Texas

Diamond Chamrock,
Dumas
La Gloria,
Tyler
Phillips,
Sweeny

10 Mb/d,U
10 Mb/d,E78

Bloomfield

Sun,

Corpus

Texas

City,

5 Mb/d,U77

Ponca
C

32.5 Mb/d,U79
Ke,E79
Re,C
To 190 Mb/d,E79
To 25 Mb/d,C

Christi
Texas

City

By 8 Mb/d,E78

TipDerary,

Zngleside

5 Mb/d,C
By 15 Mb/d,E78

Uni, Rockport
Union,

Phase:

C-Completed since 9/1/77,

U-Under

Year:

(77,

78,

10 Mb/d,E78

Nederland

Re,C

EIEngineerina,

79,

RelRevamp,

80)

a Compiled as of 1/1/78 and reported

Source:

plPlanning,

construction

Hydrocarbon

Processing,

in thousand barrels/day

1978.

4-5

(Mb/d)

TABLE4"2 (Concluded)
REFINERY
GROWTB
1977-1980a
REPORTED
PBEDICTIONS
OF
Co.

FCC _

CompanY
/CitY

EPAReRion~
ReRion VTZ

Boiler

Refi~E

To 9 Mb/d,U79

CRA,phillipsburg

KansasNebraska

Missour

None indicated

ji

Ohio

~8~
Oary

Colorado

None indicated
Amoco~ Mandan
None indicated

Montana

North
South

ToLO
Wbld.U78

F~uita

Western,

Dakota
Dakota

Utah

Little

Wyoming

Bmerica,

17Emld,E78

Gasper

Mountaineer,

//

By4.2Hbld,PBO

L8 Barge

ReRion IX
Bone

Arizona

indicated

E78

Lion, Bakersfield

~,,

Hawaiian
Barbers

By7.5~b/d.878

Independent,
Point

None indicated

Nevada

ReRion II
i _

None indicated

Alaska

cc

Idaho

Cascade

Oregon

Columbia

United

Washington

Phase:

Independent,

Re,E

Seattle

C~ompleted
UP~,der

since 9/1/77, E'Engineering,

as of

PsPlanning,

RePRevamp,

construction

(77, 78, 79, 80)

Yea~:a
Compiled
Source:

so Mb/d,P

Energy,

1/1/78

and

reported
in thousand
barrels/day
(Mbld)

Processing,
Hydrocarbon

1978.

4-6

'I

4.2.1

Fluid

The fluid
heat

boiler

since

be

and

as

the

with

at

is

particles

present.

electrodes

where

based

will
of

carbon

waste

and carbon
together

monoxide

and they

settle

will

they

collected

a gravity

settling

The precipitator

of the emitting

matter,

the

particle

On FCC unit
mounted
plates.

from

regenerators,
box con-

A corona

discharge

their

charge

chamber

to the

to the plates

mechanism
plates

the

steel

then drift

the

1973a).

knocks

these

and electrodes

or hopper

from which

discarded.

efficiency

voltage

agglomerators

A rapping
free

and

particle

particles

particles

remain

fine

transfer

agglomerate.

(EPA,

matter.

grounded

gaseswhich

The charged

technology,

particulate

a horizontally

opac-

electrostatic

for

chamber.

and

of

NSPS for

precipitators

are

generally

use

control

technology

ionizes

into

the

electrostatic

settling

they

The present

on

demonstrated

electrodes

agglomerated

are

best

a gravity

electrode

larger,

be discussed

Control.

precipitators

positive

the

matter

Matter
was

control

precipitator

taining

matter,

Control

new innovations,

Electrostatic

the

particulate

same.

matter

demonstrated

combined

the

Particulate

precipitators

best

are

particulate

Even with

opacity,

and regenerator

separately.

4.2.1.1
ity

regenerator

and particulate

controls

discussed

cracker

NSPS for

Opacity

the

Cracker

catalytic

have

monoxide.

Catalytic

drift

is

electrodes,

dependent

on:

the resistivity

velocity,

the

4-7

collector

the

effective

of the particulate
plate

area,

or

1'
the plate rappingcycle, and the velocity, residencetime and flow
rate of the gas stream. The primary design parameter is the collec-

tor plate area. Operating parameters include electrode voltage

i'

adjustment,
platerapping
cycle,velocity
distribution,
andammonia
injection

to reduce particle

resistivity

Moderate changes in FCCregenerator operation will not affect

the precipitator efficiency. However,changesin catalyst (affec~ing

II

particle resistivity), flue gas flow, or particle size can affect

efficiency significantly.

Particle size is of particular importance.

As particle size decreases, the efficiency of the precipitator

decreases,

Figure 4-1 shows the effect of particle size on the

efficiency of an electrostatFc precipitator

The particle drift

velocity (v) is proportional to particle radius. For any given plate

sire, efficiency will decrease as particle size decreases. This is
a very important consideration whendesigning precipitators for FCC
regenerators built or retrofitted with modern,high efficiency cy!j1

clones and separators that can removeessentially all particulate

matter greater than 15 micronsin diameter(Krueding,1975). Other

parametersaffectingparticle drift velocity, suchas electrodevoltage and gas velocity are controlled to increase the drift velocity of
the smaller particles.

Precipitators for FCCregenerator emissions

are currently designed for gas velocities of 5 to 6 feet per second

and 21 t~ 27 feet of gas travel for 80 to 95 percent removal effi-

i ii

ciency;gasvelocitiesof 3 to 4 feet persecond

and30to 36feet of
4-8

99.9

99.8

99.7
99.6
99.5

99.4

7!

99.0

4~

98

I
~

97 ~

o:
,

95
94

's

"w

o.

93

92

s~
80

70

02

60 ~--

W ~ drift

velocity

(m/sec)

50
40
30

20

YO

40

50

60

70

COLLECTOR
PLATEAREA(m2)/GASFLOW(acm/s)
Source:

American

Petroleum

Institute,

1978.

FIGURE

EFFECT

OF PARTICLE

4-1

SIZE ON COLLECTION

EFFICIENCY OF AN ELECTROSTATIC PRECIPITATOR

4-9

80

90

--:. s

gas travel for 95 to 99 percent removalefficiency; with a distance

of 8 1/2 to 9 3/4 inches betweencolector plates

Plate tapping is

done approximatelyevery four hours (AmericanPetroleumInstitute,

i:

1978).

Cyclonetechnology
is integral to the operationof a FCCunit.
Theprimarypurposeof the cycloneis to return entrainedcatalyst to
the fluid bed. Kultiple cyclones in series are used in the reactor

~j

andthe regeneratorto reducethe loss of catalyst. Thesecyclones

are internal to the process unit and, therefore, cannot be repaired
without suspending operations.

Deterioration of the cyclones is an

importantfactor in determiningthe operatingperiod of an FCCunit

since most units operate for more than two years before shutdown.
A cyclone is a centrifugal dust collection device with a tangential opening through which a particle carrying gas stream enters a

cylindrical barrel at high speed. Thegas streamIs givena downward

spiral whichforces the particles to the outerwall of the barrel and

downwardto a dust hopper. The "cleaned" gas stream then exits

throughthe center of the top of the barrel while the collected

particles return to the fluid bed through a dipleg. The exhaust gas
stream then passes through a series of one or moreadditional cyclones

prior to its exit fromthe regenerator. Athoroughdescriptionof

cyclonetheory is beyondthe scopeof this report For morecomplete
:i

ii

information, refer to the ~anual on Disposal of Refinery Wastes,

VolumeOnAtmosphericEmissions(AmericanPetroleumInstitute, 1978).
4-10

II

There

cyclones

are

Catalyst

Particle
size
exponentially

attrition

Particle

Catalyst

that

impaction

loading

- particle

defined

of fine

in

diameter),

results

in the first

in most

in the

bed

in

the

reactor.

an equilibrium

size

less

with

collection

than

from.

than from

bed.

Catalyst

attrition

catalyst

is

occur

through

the fines.

required

to

the

The bed

which can consist

40 microns

efficiency

and gas stream

decreases

than 5 microns
ciency

percent

exclusively

(American

of as

Petroleum

1978).

The particle

tially

reaches

(particles

rather

Losses

inventory

particle

increases

cyclone

and makeup

of collecting

eventually

of fines

catalyst

cyclones which are incapable

Institute,

decreases

efficiency

almost

stage

installations,

fluid

much as 30 weight

particles

collection

as the production

of particles

the

from

loading.

of particles

observed

emissions

- particle
collection
efficiency
with decreasing
particle
size.

44 microns

the breakdown

affect

1978):

- production

increased

attrition,

than

maintain

factors

(American Petroleum Institute,

with

is

important

less

three

increases

as a 60 percent

pass

loading.

in particle
through

with

Efficiency
until

uncollected.

gas stream

increase

size

of a cyclone

loading.

in efficiency

4-11

is affected

decreases

exponen-

all

less

nearly

On the other
This

by

fines
hand,

effi-

can amount to as much

in a cyclone

operating

at 35

percent single particle collection efficiency at no load (< 1 grain

solid/cubic

]I;
ii

foot gas) when increased

to a load of 1,000 grains

solid/cubic
footof gas(Amel-ican
Petroleum
IusriCute,
1978).

Filters havebeenusedfor the collectionof particulatematter

throughout

the industry.

There are various

depends on the particular characteristics

cleaned.

:!11
~1

Filters

may be:

flexible

types and their

use

of the gas stream to be

tubes,

bags, or sheets

of

material; semirigid supported fabric or mats of fibrous material;

fixed or packed beds of granular particles;

and/or fluidized

or

moving
bedsof granulesor fibers. Pertinentgasstreamcharacter!'I

istics

are particle

and flammability.
the

suitability

size, temperature, moisture content, corrosivity,

Collectively,

of

a filter

these characteristics

will

determine

medium.

The theory of filtration

for particulate

matter control is that

collection

of particles

in the micron range will take place by:

Impaction - of the particle

on the filter

medium due to

inertial

impingement as related to gas stream velocity and

particle

size

Interception
- of the particle by the medium due to the
size of the particle with respect to the pore size of the
medium

Diffusion
- of extremely
movement which increases
the

filter

small particles
the probability

due to Brownian
of contact with

medium

Miscellaneous-

mechanisms

such

as electrostatic

forces,

thermal effects
on agglomeration
and Brownian movement,
and sedimentation
of heavy particles
in low velocity
gas
streams

due

to

gravity.

4-12

The

filter

medium

can

be

order

to maintain

filter

efficiency

increases

filter

medium.

As efficiency

to maintain
cleaning

gas flow.

gas

flow

is

becomes

the

matter
collected

increases

of

medium

by gentle

not cleaned

is

vacuum

in

is collected,

the

point

acts

energy
is

as a

required

reached

where

required.

shaking

but are

or

material

however,

A trade-off

the

pressure

or reverse

replaced

gas

flow.

when the pressure

drop

excessive.

Filters

are

the

especially

for very

efficiency

is

FCC

under

As particulate
because

achieved

Beds are usually

either

increases.

or replacement

Cleaning

used

unit

efficient

that

matter

particles.

however,

can be used

fabric
would

from

be

such

The sequence
technology

to

flue

filters,

and

remove

gases.

they

can

unsuitable

corrosivity,

disadvantages

(sub-micron)
high

matter
as

scrubber

particulate

control

The cost

few filters

are

device,

of this
used

on

regenerators.

as particulate

content,

efficient

small

relatively

Wet Scrubbers

streams

most

as

cost

be

Conditioning
- the
occurs
between
the

Although

scrubbers

or

particles
particle

4-13

for

many

filters

sludge
from

as well
are

not

as

gaseous

due

flammability.

particles

summarized

used

fabric

and resulting

of removing
can

pollutants

be

for

temperature,

gaseous

to

moisture

Scrubbers

have

disposal.

a gas

stream

by using

as:

so that a high
and liquid

degree

of contact

Separation
using

- of the particle/liquid

cyclones

or impingement

from the gaseous stream

baffles

Removal - of the particle/liquid

as a slurry that can be disposed
recirculation

to

the

from the scrubber, usually

of as is or dewatered for

scrubber.

Comparisonsof the various particulate matter control technologies have been madeby the AmericanPetroleum Institute
In Table 4-3, relative

cost, particle

size collection,

(1978).

pressure drpp,

and energy consumption are compared for the four types of control

i:

equipment previously discussed.

Filters

and electrostatic

tators are capable of removing the smallest particles,

precipi-

but the

i:

precipitators
havea substantially
lower
pressure
drop.Single
stage

cyclones, spray towers, and electrostatic

precipitators have the

lowest power consumption and the lowest relative

cost including

auxiliaries.

Data on the particle

trols

II

collection

are shown in Table

have the highest

4-4.

overall

efficiency

Fabric

efficiency

filters

and venturi

con-

scrubbers

(American Petroleum Institute,

1978). Manyof the controls discussed show a Iramatic decrease in

efficiency when collecting
the particle
in diameter.

collection

smaller sized particles.

efficiency

It is apparent

of particles

from this

micron)

collector

particle

variables

emissions.

The effects

on particulate

matter

4-14

Table 4-4 shows

5, 2, and 1 micron

data that the FCC unit regen-

erator cyclones are incapable of significantly

1~

of the various

reducing small (<5

of dust,
control

gas stream,
equipment

and
are

TABLE

4-3

APPROXI~ATE
C~y~CTERISTICS
OFDVST
AND
HIST
COLLECTION
E9UIPMENT
Paver

Relative
Eauipment
Cyclones:

Smallest

CaaC"

nultiple
Electroscatic

3-6
precipitators:

One-stage
Tvo-atage

Filters:

Collecteg

(picmns)

15

1-2

Single

Particle

s-XI

(o.l

2-6

<0.1

3-20

Tubular
Reversejet

Envelope

7-12

<0.1

3-20

Pressure

Drop

(inches
of

y"ed

Vsed

(kilovatt

1000cubic

per
feet

per

Remarks

pinure~e

nSY"'"'

0.1-3

0.1-0.L

2-10

0.5-2

0.1-05

0.2~0b

0.1-0.3

0.2-0.4

Compact,air conditioning service

2-6

d.5-1.5

Nigh
efficiency,
temperature
andhumidity
limiB

0.7-1.5

~ore compact,constant flou

2-6

Sl~p]el
~n.~cneiM.
~'' .idely
used
Abrasion and plugging problems

HIBh
"ffiel.n~y,
heavy
dufl
e~mslve

Limited capacity, constant flov possible

2-6

0.5-1.5

0.1-0.5

0.1-0.2

Lovvateruse

,~u

2-10

Bi~h-~l.clq
8'~rr~
h~gher
~rc~u~
(40 to 70 inches)
vill remove

VI

Scrubbers:

Spraytover
Jet

Venturi

1-2

10

4-10

4-~

2-10

Pressuregain, high-velocityliquid jet

drop

submicron-sized

particles

Cyclonic
Inertial

3-10

2-8

0.6-2

Hodified
drycollector

4-10

2-15

0.8-8

Abrasion
problen~s

0.6-2

Channeling

2-10

Abrasion

Packed

3-6

Rotating impeller

4-12

fncludes

auxiliaries.

bWith90-95 percent efficiency (weight).

CIncludeapressure loss, vater p~ing.
Source: American Petrole~m institute,

and electrical energp~

1978.

0.5-10

-c.

problem
problem

-----*n.~-.
.._II_

'------C------~~'

TABLE

4-4

PARTICLE COLLECTION EFFICIENCY

Overall Efficiency
Collection~e~
Cyclone;

(percent)

65.3

medium-efficiency

Cyclone;
high-efficiency
Cyclone,

84.2

irrigated

Electrostatic

precipitator

Fabric

filter

Spray

tower

Scrubber;

wet

Scrubber;

self-induced

impingement

Scrubber;

ventuti

spray

Dieintegrater
Source:

American Petroleum

Institute,

Efficiency at 5u

(percent)

Efficiencyat 211
(percent)

27

14

91.0
94.1
99.9
96.3
97.9
93.5
99.7

73

87
92
>99.9
94
97
93
99.6

4h

98.5

98

95

1978.

60
85
99.9
87
92
75
99

Efficiency

at 1~

(percent)_
8
27

42
70
99
55
80
40
97
91

_,g~i~

summarized
factors

in Table

due

to

Carbon

require

(volume)

of

the

Carbon
carbon

contains

dioxide
situ

the

heat

plete,

the

using

increase

is

0.18

attributable

from

the

monoxide

removed

fuel

is
or

oxidation

generally

regen-

(Murphy

reduced

in

the

regen-

reaction

as

steam.

water

wall

to maintain

by

is

boilers

firing

using

temperatures

of CO to CO2 is essentially

using

CO boilers

the

boiler

matter

or liquid

calculated

standard

raising

is

are

monoxide

a CO boiler
The

The oxidation

solid

Regenerator
either

boilers

particulate

to

matter

in

generated

from

gram of particulate

late

FCC unit

com-

do not have difficulty

NSPS.

Increased
boilers

for

carbon

of carbon

either

and FCC regenerators

meeting

NSPS

from

10 percent

and an auxiliary

of 7000C to 7600C.

gas

combustion).

monoxide

monoxide

The

The flue

The emission

tin
and

requirements.

Control.

gases.

carbon

itself

exothermic

Monoxide

limiting

an uncontrolled

1977).

erator

regulatory

are

flue

and

to

variables

not exceed 0.05 percent

typically

oxidation

or

these

that carbon monoxide emissions

regenerator
Soudek,

Many of

equipment

4.2.1.2

erators

4-5.

fossil
the

matter
auxiliary
for

emissions

are

permitted

fuels

as auxiliary

heat

value

of

per

million

fuel.

the

a six-minute

period

The
fuel

of heat
from

permits

CO

fuel.

auxiliary

calories

An exemption

from

the
soot

as

input
particu-

blowing

tubes.

in
the

situ

combustion

temperature

in

of
the

4-17

carbon
regenerator

monoxide
or.by

is

achieved

using

a CO

by

..

~ ~- ..(;1.1

...:.

;:i------

::*?~~

lABLE

4-5

EFFECTS
OFVARZABLES
ONDUST
COLLECTION
High-Efficiency

Yariable
-------c~

Cyclones

~L~k-

Effect of DustVariations:
Efficiency, p8rticles:

Poor

<1 micron
1-10

micron

10-20
micron
,20
micron

Poor

poor to Fair

Poor

Good

Fair to Good
Fair

Abrasion

Poor

Good
Fair

ELectrostatic
precipitators

Good

Good

Good
Good

Good

resistance

Ability to handle sticky, adhesive

Fair

materials

Poor
Yes

Bridging
matetialsBiMLlouble

Slight

Fire or explosionhazardminimized
Canhandlehygroscopic
materials

Fair
Yes

large foreign materials cause

Seldom

Yes

400

400

Fair
Fair

Poor
Yes

Poor
WithCare
Yes

Collectors

Good

Good
Good

Wet

Fabric

Collectors

poor
to fair,
Fair to good
Good

Good

Good

Good

Good
poor

Poor

to

good

No

Yes

Good

Poor

Yes

WithCare

Seldom

Seldom

to

yes

plugging
r

01

Effect of Gas Stream Variations:

E(aximum
temperature(C),
standard

construction

Troubles fromcondensedor entrained

mises

400

or

Corrosive
construction

slight

Considerable

vapors
gases

No

limit

Slight
Severe

attack

slight

standard

Collector:

Large

Space

Preaaure
drop(Inches
ofvarer)
p.educed volume adversely
collection

Some

Considerable

82-135

affects

1-2
inches
Yes

EIIBC

Sl(~hT

Modest

Large

3~5inches

Yea vith n~st

designs

efficiency

"\lenturi scrubbers are considered good

bFilters for highertemperatures

are available

Cp,,asure
dropforventuri
scrubbers
i. i" Lherompof10to 7Dinches
of~~acer.
Source: AmericanpetrolelrmInstitute, 1978.

1-2

inches

No

511ehr
Hodest to large

nodeaf

1-6 inches

)-6 inchesc

No

Depends

design

on

combustion

promoter

generally

requires

that

standing

continuous

FCC unit

regenerator

Increasing
beneficial

such

the

formation

emission

reported

(Rheaume

et

Carbon

oxidation

ation

i.e.;

catalysts

oxidation
tional
shows

due

carbon

reducing

the

regenerator

an

older

a number

to

carbon

carbon

from

and particulate
It

does

not

as the

monoxide

emissions

high

dioxide,

removal

standard,

Carbon

of

The decreased

monoxide

matter

catalysts

the yields

temperature

are

the

carbon

from

regenerator
exothermic,
will

three

raise

capable

affect
allowable
have

regeneration

on regenerated

temperature

the

is

FCC regenerators

used

these

Because

catalyst

temperature.
to test

If

regener-

high temperature

reduced.

oxidation

operating

by improving

using

the

In addition,

catalyst.

already

adding

of promoting

dense bed.

of gasoline

4-19

-----------

coke

unit.

when using

oxidation

increase

of CO is

data

of

on catalyst.

burn-off.

of with-

in

has

to greater

formation

are added to a regenerator

regeneration,

feasible

regenerator

of CO to CO2 in the regenerator

catalysts

be capable

which

1976a).

monoxide

these

combustion,

constraints.

combustion

particulate

as negligible
al.,

not

FCC regenerator

coke

situ

unit
is

the

overall

the

the

on

in
to

coke

from

based

7600C,

yields

the

in

of metallurgical

addition

reduces

to meet
is

at

gasoline

emissions

ability

been

in

often,

FCC regenerator

temperature

and decreased

matter
the

the

because

increased

catalyst,

Very

operation

effects

as,

coke

catalyst.

the

to a convenTable

a CO oxidation

4-6

TABLE 4-6

USEOFCARBON
MONOXIDE
OXIDATION
CATALYST

I~

Unit

~E~f~l~m~fl

~----~~

Unit

Unit

4a

6a

Regenerator:

i/

1,

Dense,OC

1325 1303

1336 1926

1156

Dilute,OC

1333 1304

1362 1324

1154

Cyclones,OC

1450 1405

1370

1321

1375

1325

Fluegas,OC

1422

3.6

0.3

0.05

0.05

Flue gas CO, vol %

NSPS Standard,

vol %

I - conventional

2 - CCA-22 with

j!

catalyst

O
0.05

0.05

catalyst

mixture

3 - CBZ-1catalyst
4 - CCZ-22
5 - DHZ-15
6 - CCZ-22

catalyst
catalyst
catalyst

a CCZ-22.carbonmonoxideoxidation catalyst
Source:

Rheaumeet al.,

1312

1342

9.3

0.4

1370

conventional

1296

1976.

4-20

0.05

0.05

catalyst.

Carbon

depending
4.2.2

on the

Fuel
The

NSPS

sulfide

in fuel

gas

of

sulfur

gases.

This

for

be

sulfur

in

fuel

is

controlled

dioxide

gas

also

dioxide

can

reduced

to 0.4

percent

or less

Device

The standard

removal

were

temperature.

Combustion
standard

furization.

levels

operating

Gas

of hydrogen
sulfide

monoxide

limits

burned

at

emissions

tlydrogen

stripping

and hydrodesul-

as an alternative,

from

accomplished,

concentration

a refinery.

by amine
permits,

the

for

the

fuel

example,

by

the

direct

gas

burner

stack

use

of

scrub-

wet

bers.

Amine gas

treating

solvent

processes

process

in petroleum

and

hydrogen

absorber

unit.

dry

1975).

sulfide

in the refinery.

less

than

gram of sulfur/100

1975). The acid-rich

R2S is

piped

recycled

to

DEAsolution

or still.

to a sulfur
the

absorber

The

sour

H2S-free

The treated
scm of gas

unit.

4-21

refinery

gas con-

DEA in

are

an

removed

gas is then used as

gas will
(Gary

is regenerated

unit.

common

(DEA) process

dioxide

The steam is condensed

recovery

most

contacts

and carbon

gas and the treated,

elsewhere

in a regenerator

dioxide

sulfide

and physical

diethanolamine

process,

carbon

fuel

0.57

the

In this
and

chemical

processes.

is

The hydrogen

from the refinery

include

absorbent

refineries

(Gary and Handwerk,

taining

processes

usually

contain

and Handwerk,

by steam stripping
and the separated

The regenerated

DEA is

Hydrotreating
canbe appliedat anypointin the refineryprocess

stream

It

is

applied

to

a wide
variety
offeedstocks
ranging
from

reduced
crudeto napthasandis usedto stabilizeproducts
and/or
remove
undesirable
elements
in feedstocks
by reactionwithhydrogen

ii!

Hydrodesulfurization
iS theremoval
of sulfurfromfeedstocks
by
catalytic

reaction

with hydrogen~

The feedstock

is mixed with

hydrogen,
heated,andpassedovera catalystwherethe hydrogen
I

reacts with sulfur in the feedstockto formhydrogensulfide.

sulfide fuel
Excess hydrogen
is recoveredand recycledand a hydrogen

gas stream

iii

Fi
II

11;
I;

I.j:

4\

is steam

distilled

from the feedstock

The fuel gas

streamis sent to an H2Sremovalunit andthe desulfurizedproduct

Any
fuelgasgenerated
from
further
processing
willbeverylowin hydrogen
sulfideSinceall products
is ready for further

processing

of this feedstock
are also lowin sulfur, the useof hydrodesulfurization has significant effects outside the refinery

~~~
~_~~_
_~~,~~~
_~,,,,,.,,,,,,~,, ,, ..,..,,

the controlof particulatematteremissionsTheremoval

of sulfur
dioxidefromflue gasesis the subjectof a significantamount
of
currentresearch Processes
nowin commercial
useare: ammonia
scrubbing,
lime-limestone
slurryprocesses,dry limestone
processes,
andthe Wellman-Lord
process(sodium
sulfite scrubber) At least one
proprietary

process

using an aqueous

caustic

solution

is being used

onanFCC
unit regenerator(American
Petroleum
Institute, 1978)
Thereare no knownexamplesof S02scrubberson processheater
exhaust

streams~
4-22

4.3

Achievable

The
sulfur

Emission

emission

levels

dioxide

discussed

4.3.1

the

regenerators

for

the

EPA Regional

tested

for

new

coke

burn-off.

actual

the

of

currently

tors

equipped

with

electrostatic

the

as

than
the

control

best

to

the
is

are

are

emission

insufficient

data

with

demonstrated

time.

particulate
based

to

determine

Table

4-7

indicate

matter
on data

4-23

the

shows

regenera-

the

burn-off.

more

emission

Since

attractive
they
considering

ecoare

considcost

from FCC regenerators.

emission
from

permitted
typical

oil

kg

matter

that

can reduce

scrubbers,

emissions

matter

1 kg/1,000

data

technology

the

of

These

venturi

been

particulate

on particulate

coke

have
of

data

control

matter

which

test

kg of

data

offices.

of

significantly
or

little

a shortcoming

presentstandard

1.0 kg/1,000

is

units

precipitators

systems

boilers

devices

is

by EPA Regional

deterioration

of particulate

monoxide

and

regenerators

There

is

The

electrostatic

filter

The additional
carbon

used

than

precipitators

nomically

standards.

compliance

matter

FCC unit

This

there

cyclone

monoxide,

combustion

on operational

FCC regenerators.

of particulate

ered

being

less

available

from

the

Matter.

However,

effect

emissions

of

Particulate

to

gas

from

compliance.

system

can be controlled

fuel

achievable

offices

source

reporting
4. 3. 1. 1

and

carbon

Cracker

each

within

matter,

section.

levels

discussed

present

particulate

Catalytic

emission

be

of

following

Fluid

The
will

from

in

Levels

from
or coal-

for

TABLE

4-7

COMPLIANCE
TESTDATA
FORpARTICULATE
MATTER
Particulate

Refinery

Matter

(kg/1000kg coke burn-off)

Champlin Petroleum
Tx.

Co.,

(1977)

Run

81

Run

1~2

Run

~3

1.35
0.91
0.76
1.01

Average

NSPS

Source:

1.0

Standard

EPA, 1978.

4-24

fired
be

boilers.
reduced

There
below

4. 3. i. 2

this

no data

Monoxi~.

use of regenerator

in situ

Fuel

Gas

reduction

of carbon

it

gas to less

dioxide

4.4

Special
4. 4. 1

emissions

the

State

from

4-8.

It

is capable
The

zero percent
1976).

the

combustion

from the fuel gas by

data on achievable

to reduce

concentrations

of

It is apparent from these

the 828 concentration

Using Control

of fuel

Technologies

Scrubbers

It has been reported

in

on

230 mg/dscm.

Problems
Wet

car::

by volume.

to nearly

by removing sulfur

The available

than

for

Device

sulfur

is feasible

data

(Rheaume et al;

828 in fuel gas are shown in Table 4-9.

that

can

monoxide with or

can reduce emissions

of fuel gas is done primarily

data

test

than 0.004 percent

combustion

Combustion

of

amine stripping.

emissions

is shown in Table

at a high enough temperature

4. 3. 2

that

the carbon monoxide boiler

to less

promoter catalysts

The

The compliance

from these data that

if operated

substantiate

from FCC regenerators

of reducing CO emissions

without

to

level.

Carbon

monoxide emissions

is apparent

is

of Alaska

that
(EPA,

it

is not possible

1978a).

Although

touse
this

wet scrubbers

could

affect

compliance with National AmbientAir Standards or possibly state

standards

should
refineries.

for

the

not affect

reduction

of sulfur

compliance

The best

available

with

dioxide

emissions,

the current

NSPS for

control

4-25

technologies

this

problem

petroleum
considering

cost

TABLE

4-8

COMPLLANCE
TESTDATAFORCARBON
MONOXIDE
Carbon

Refinery

I/

(Vol

Champlin ~etroleum

Co.,
II

Run

~2

Run

~3

(1977)

Tx.Run
0.00306
0.00353
0.00330

Average

NSPS

II

Source:

Monoxide

0.05

Standard

EPA, 1978.

I/
: Pr

;Ijj

I;
4--26

%)

TABLE

COMPLIANCE

-TEST

4-9

DATA

Refinery

FOR

SULFUR

DIOXIDE

H2S
(mg/dscm)

Mobil

Oil

Delta

Refining,

Hill

Petroleum

Marathon
Getty

Oil,

Refining,

Standard

NSPS

Co.,

Oil,

N.J.
TN.
Co.,

LA.

(1977)

137

(1976)

LA.

(1977)

81

(1977)

121

KA. (1976)

65

CA. (1976)

229"

Standard

230

*reported as "typlcal analysis = 0.1 gr H2S/dscf"

Source:

EPA,

1978.

4-27

are
f

electrostatic

situ

precipitators,

combustion,

sible

for

NSPS as

and amine

petroleum
it

is

either
strippers.

refineries

unlikely

CO boilers

in

that

It
Alaska

climatic

or regenerator

should,
to

therefore,

comply

conditions

with

will

the

in

be poscurrent

affect

these

of

particu-

controls.

jj

4.4.2

It

late

i:

Condensable

has

been

matter

using

1978).

reported

measured

in situ

EPA,

Particulates

that

by EPA Reference

combustion
Since

a significant

tile

portion

Method

is condensable
definition

5 from

matter

the

FCC regenerators

(Huddle,

of particulate

1978; and

matter

is

" ...any

/I:

finely
divided
solidorli~uid
material,
arller
thanuneombined
uater.

jl!

as measuredby Method5 of AppendixA to this part or an rqllivnlent

ii

or

alternative

is

collected,

The

problem

mist
is

in
very

late

.j
ij

test
tests

but
appears

(40

the

catch
report
performed

CFR 60,2(V)),

measurement
to

Reference

hygroscopic

matter

pliance
ical

the

method"

be

caused

Method
and

by

5 probe

water

after

of

of

1978)

the

Tile
states

on a particulate

difficulty

is

particulate

the

matter

condensation

and

filter.

hydration

drying.

(EPA,

the

the
catch.

with

Petroleum
results
The

of

acid
the

results,

acid
mist

part~cu-

Company
varioris

what

catch.

sulfuric

Sulfuric

remains

Cllamplin

of

not

comanalyt-

summarized

in Table4-10,showed
that over50percentof the me.7surcd
Re[erencf
Method
5 particulatemattercatchis otherthancatalystfines.

4-28

TABLE

CONDENSABLE PARTICULATES

4-10

FROM FCC UNIT REGENERATORS

TEST

ASME instack

RESULT

filter

89% less
Method

NaOl titration

of Method5

matter

50Z H2S04

catch for H2S04

Thermal.

particulate
5

analysis

of Method

60% weight

analysis

of

64I

loss

catch

Sulfate

Method

sulfate

catch

X-ray spectrograph
of
5 catch

27I II2S04in probe wash

Method

Source:

EPA,

1978.

4-29

t~,~

4.5

Energy Needs an d En vi ro nmental Effects

---

Energy consumptionhas always been a

factor

in the economics of

,~,.,~.~.~.~.~
-~--- ' '-' cern,

Because petroleum

refineries

use app

roximately

10 percent

of

the crudefeedstockfor energyrequirements

withinthe refinery

j:

itself, reductionsin this energyuseare of interest frombothan

economic
andsupplyviewpoint Energyconsumption
in FCCunits can
be reducedthroughthe use of carbonmonoxide
oxidationpromoter
catalysts and energyrecoveryexpansionturbines.

~jjll

New
technologies
that will reducethe emission
of pollutantsto
the atmosphere are of national interest

These technologies

are of

interest to industryas well becauseof government

regulations,
environmental
concern,andveryoften, excessiveemissionsare an
indication of inefficient
4.5.1

process operations-

Expander TechnologY

Expander
turbines
areusedto recover
some
of theenergy
usually
lost

in the FCC regenerator

The amount of energy

flue gas,

that

is

actuallyrecoveredis dependent
on the inlet gas temperature,gas
flow rate,

and the pressure

drop.

Barbier

(1977) has estimated

that

the maximum
recoveryis approximately
45kcal/kgof flue gas, In

1973,
thelargestinstallation
waSrecovering
15,500
horsepower
from
.FCC unit

installed

at a Martinet,

California,

refinery

in 1966

(Braun,
1973).
Sincethattime,expanders
as largeas 22,000
hphave
beeninstalled(C.F.Braun
&Co.,1976).Today,
anestimated
20,000
4-30

hp can be recovered
Gas

Journal,

from

fac'tors

units.
destroyed

early

ence

show that

virtually

must

has

the

efficiency

with

time,

percent

catalytic

but

test
all

cracking

unit

of the

the

turbine

(Oil

this

and

matter

of

turbine

five

due

years,

to

is

of

the

startup

10

acceptable

limits

catalyst
reduction

turbine

can expect

the

experi-

than

a slight

erosion

under

greater

of third-stage

refineries

recovered

by catalyst

within

There

energy

and commercial

erosion

problem.

of the

blades

Experiments

The development

this

energy

installation

particulate

to keep

solved
the

of

units.

1977).

after

influenced

erosion

be removed

(Murphy and Soudek,

separators

have

First,

fines

microns

average

1977).

'Itro limiting
recovery

the

in

blades

to recover

conditions

95

(Barbier,

1977).

The other
art

turbines

gas

temperatures

bustion

cannot

use

from

can reach

ous operation
must

limiting

tricity

for

obtained
This

level

investment

gases

over

blower.

passing

at

the

of savings

(Barbier,

Without

through

the

power

is

yearly

a 1.8 year

1973).
4-31

state-of-the-

1977).
total

this

Since

flue

in situ

capable

com-

of continu-

capability,

gases

expander.

is generally

Oil Company refinery

yields

with

and expander

by the expander

refinery.

Present

operating

required.

Any excess

at the Shell

(Braun,

6800C

7600C a separator

before

use

temperature.

regenerators

The power recovered

air

is

at 7600C are

be cooled

FCC unit

factor

used
savings

to generate

elec-

of $685,000

at Martinet,
payout

used for the

were

California.

on a $1.?5 million

4.5.2 Carbon_Monoxide
OxidationCatalysts

Carbon
monoxide
oxidation
catalystswereintroduced
in theearly

1970's
asanalternative
to thezeolitecatalysts
being
usedin fluid

catalytic

crackers.

5pical

of

these catalysts

com-

bustionzeolite(PCZ)
andcomplete
combustion
zeolite(CCZ)
series
Davison

catalysts offered by W.R.Graceand Company,

jl

are the partial

During

their

first

commerc

Chemical Division

ial trial in April1975,CCA-44

wascharged

t,.FCCunitoperating
withhigh-temperature
regeneration
It is
estimated
thattherearenow(1978)
12FCC
unitsusingCO
oxidation
catalystsand12more
usingCOoxidation
additives
(Wallendorf.
1978),

ThePCZ
catalystspromote
partialcombustion
of carbon
monoxide

withanincrease
of 170C
to 280C
in theregenerator
andareparticu-

larlyuseful
where
themetallurgy
oftheregenerator
limitstheallowable

operating

limiting

factor,

temperature

CCZ catalysts

Wherethe temperature increase is not a

can

be used to promote complete com-

bustionof carbonmonoxide
in the densebedwitha regenerator

temperature
increase
of approximatelY
560C.Thisincrease
in

regenerator
operating
temperature
is generally
accompanied
bya
reduced
cyclone
temperature
sinceCOoxidation
nolonger
occurs
in
thecyclonesOnlyin thecaseof replacing
catalystsunderconventionalregeneration
conditions
withCCZ
catalystsis the temperature
increasedin both the regeneratorbed and cyclones~

4-32

The advantages

Reduced

cyclone

erator

in

held

of using

in

Reduced

temperatures

situ

the

CO oxidation
when

combustion

since

regenerator

excess

in the dense
more efficient

air

dense

with

oxidation

rates.
the

gas volume
coke

on

off

more of the

the

amount

of

the

because

burning

coke

is promoted

the cyclones,
the reduction

The
erosion

combination
of
of the cyclone

and particle

loading.

formed

formed

13

activity
promotes
air
requirements

through
permits

regenerated

coke

regen-

reaction

bed.

requirements

circulation
should
reduce

Decreased

operating

bed and increased

catalyst
use of air.
The reduced

of decreased

are:

the

should
decrease
the gas volume
the increased
catalyst
activity
catalyst
effects

catalysts

catalyst

in
in

the

the

due

reactor

first

and
of

these
because

to

burning

and reducing

place.

The

less

coke on the catalyst,

the higher
the catalytic
activity
and the greater
the yield
of useful
products.
PCZ and
CCZ catalysts
are approximately
40 and 150 times more
active,
respectively,
than conventional
catalysts
(Rheaume
et

al.,

1976).

The use of torch

oil may be discontinued.
often
used in the regenerator
to maintain
perature

for

in

situ

carbon

monoxide

combustion.

The emission
of carbon monoxide is reduced
although
the
actual
emissions
are dependent
on the temperature
maintained
in the regenerator.

The only
catalysts
heat

required

Torch oil is
the high tem-

is

value

disadvantage
on those

of the

to

the

FCC units

carbon

use

of carbon

presently

monoxide

must

using

monoxide

oxidation

a CO boiler.

be made up using

The

an alternate

fuel.

4.5.3
Some

on the
stripping

Sulfur
of

surface
is

the

Dioxide
sulfur

of
used

the
to

in

Catalysts
the

catalyst
remove

FCC

feedstock

during
entrained

4-33

the

is

cracking

hydrocarbons

retained

in

process.
from

this

the

coke

Steam

It

This leaves a sulfur/coke

deactivated
catalyst
priorto regeneration
covered catalyst

for regeneration

During the regeneration

process,

the cokeis oxidizedto COandCOp,andthe sulfur to SOx,primarily

S02, The sulfur

content

of the coke is directly

related

to thesulfurcontent
of thefeed It iS estimated
thatuncontrolled
emissionsof SOxfromFCCunit regeneratorsin the U,S.average

805ppmandmay
beas much
as 2,750
ppm
when
high-sulfur
feedis
1,

processed
(Vasalos
et al., 1977).
Amoco
Oil Company
has developed
a newUltraCatcrackingprocess

which
reduces
sulfuroxideemissions
fromFCC
unit regenerators
The

process
usesa newcatalystthatretainssulfuroxides
onthecatalyst
andreturnsthemto thereactorwhere
theyareremoved
withtheproduct streamIf a lowsulfurproduct
is required,the sulfutwill
be removed
byaminestrippingor hydrotreating
andeventually
recovered
in a sulfurrecovery
unit. Pilot tests indicatethat
the newcatalyst is capableof reducingsulfur oxideemissions

80to 90percentandcommercial
tests are planned
to confirm
this

-i

data(Vasalos
et al., 1977)

4-34

5.0

INDICATIONS

5.1

Test

FROM TEST RESULTS

Coverage

in Regions

In January of 1978, the Metrek Division

made a survey of the NSPS compliance test

Regional offices

(Watson et al.,

(CDS) indicated

a total

able for only nine.

matter

test

retest

is scheduled

taking

the third

ticulate

matter)

is questionable.
pending

This
et

tests

method used when

test

data,

continuous

data

for petroleum

offices

matter

monitoring

future.

that

in Table

at 1.01 kg/1,000

one carbon monoxide test

tests

in the

refineries

is presented

test

of par-

is

5-1.

kg coke burn-

at 0.0033 percent,

with averagesranging

and

from a low concen-

indications

in the CDS system

have been performed

that

a total

of

but the data

13 tests

have

that

four addi-

were not available.

been

performed

(Watson

1978).

The data
figure

of the actual

of

results

There are

indicates
al.,

review

that no

of 1.4 mg EI2S/dscmfuel gas to a high of 228.8 mg H2S/dscm

gas.

tional

particulate

and

seven hydrogen sulfide

fuel

Corpus Christi,

sample (lowest measured level

There is one particulate

tration

of compliance

EPA Region VI has indicated

at the EPA Regional

no opacity

failures

particulate

The NSPS compliance

off,

however, data were avail-

There were no reported

The Champlin Petroleum Refinery,

at EPA

The Compliance Data System

tests;

tests.

available

data available

1978).

of thirteen

of MITRECorporation

presented

of thirteen

in Table

NSPS compliance

5-2 is presented
teats.

5-1

in contrast

This fable

to this

shows the

~=L~~

TABLE

.5-1

NSPS
COMPLIANCE
TEST
DATA
- pETROLEUn
I~EF~L~ERIES
NSPS Data

NSPS
Daca
particulate

Matter

Range

Averag~_ ~a~B~.

Indlcared~alal
~gj~Number

of

Tests

performed

Carbon Monoxide

Opacity

--~2~-

-IPPBL-~g~L
Range_Average ~"~.
AVe~g~

EPA
Region
Region ii
Mobil Oil, paulsboro,
Region

fV

Delta Refining,

Sulfur Dioxide

<2.3-3.9 14

N.J.

3.7-14.0

7.3

nemphl", TN

VI

Region V

Regior VI

30.6-35.3

0.76-1.35

Champlinpetroleum,CotpUsChristi, TX

33

1.01

VIL

Region

IX

GettY Refining,

80.8

99.4-157.1 120.6

Hill petroleum, Krotz Sprink,LA

Harathon OI1, Garyville, LA
Region

58.3-1105

42.3-73.5

El Dorado, KA

50.8-1174

64.5
80.0

228.8

Chevron U.`S.A., El Segundo, CA

S~.zndard Oil,

Richr~nd,

CA
1.0

Current

Source:

~SPS

Watson et al.,

1978.

30

500

230

TABLE

CEOCRAPHIC DISTRfBlfiIC~t

5-2

OF POSS~BLE NSPS AFFECTED FACILITIES

19umbat of Icw or

EPA

Region

Completed'

I
II
III
IV
V
VI

,
1/10
4/15
11/86
16/149

Co~st~uctionb Engineeringb FluidCat

,
1(80)
l(lOA)
1(77)
1(79)

VII
VIII

IX

0/4

1(79)

7/6

1(78)

6/112

Officesc

Under

(comp.data)

(comp.date)
,
1(NA)
1(79)
1(NA)
1(78)

Clacket
(FCC)

. 50/385

FuelGas

Combustor
(FGC)

3
2
1
38

Future

Sources

(FCC/FGC)

-/1P

1U, 1P/38U, 37P

6(79)

6
1(78)

-/1P

62

1U, 1P/38U, 39P

1/3

Total

of Facilities

Reported by Regional

Catalytic CrackerI)nita
(~975-78/cap.d)

rw

Nun~er

Increased Capacity Fluid

1(77)

2(78)

1(78)
2(79)

7(79)
2(NA)

1(80)

1(1PA)

aCwtrell,

1975.

bRydrocarbonProcessing, 1978; data as of 1 January 1978.

SJatson

et al.,

1978. (U - under construction;

P - planned)

dCapacityin 103barrels per streamday.

eCDS file
Regions.

does not show any sources planned or under construction.

It should not be assumed that no new sources are planned

fgot available.

Use of these entries

varies among the
or are under construction
in this Region.

II
distribution

of possible

NSPS affected

offices have reported that

I~

The EPA Regional

facilities~

thereare twoNSPS
affectedFCC
units and

62fuelgascombustion
devices
(Watson
et al., 1978)Aliterature
search
shows
thatfiftyrefineries
havebuiltnew
FCC
unitsor
increased FCCunit capacity

duringthe period1975-1978
(Cantrell,

1975;
1978)."
Data
onfuelgascombustion
sources
is notavailable.
it is not withinthe scopeof this project to
ties are, in fact, subject to the NSPS

determine which facili-

In addition
to thedataonpresent
NSPS
affectedfacilities,
Table 5-2 presents information On
growth of these sources~

the geographicdistribution Of the

TheEPARegionaloffices reportedoneFCC
al.,

unitunderconstruction
andonebeingpl"ed (Watson
et

1978)

Hydrocarbon
processing
(1978)
ontheother
hand
reports
sixFCC
units
underconstruction
("ewor beingmodified/revamped
to increase
capacity) and eleven morein

the engineeringphasek* Againthis

datais presented
for furtherconsideration
for

a determination

of

which,
if any,ofthese
FCC
unitsmight
beconsidered
affected
facilities andhencesubjectto the NSPS.

*See
Appendix
Afordetails
anwhich
refineries
ha'ereported
growth
during this period
~*See Table 4-2 for details

on

refineries reporting future growth

plans.

5-4

5.2

Analysis

of Test

Results

There is insufficient

compliance test data in CDSto make a

judgementon the adequacyof the present NSPSfor petroleumrefineries.

The available

compliance test data presented indicates

that:

The particulate matter standard is compatible with

the present

state

technology.

The opacity standard, which was set to match the

mass standard,
of

of control

control

is

compatible

with

the present

state

technology.

The carbon monoxide standard could be changed to reduce

the allowable emission of carbon monoxide although the

present data are insufficient

to establish an appropriate

standard.

The sulfur dioxide standard could also be changed to

reduce the allowable concentration
of hydrogen sulfide
in fuel gas
will
relate
content

of

although
the H2S

more

data

reduction

feedstocks.

5-5

should be collected
which
achievable
to the sulfur

6. 0

ANALYSIS

OF POSSIBLE

This section
to

the

approach

NSPS by examining

monoxide,

sulfur

economic,

of the

control

emission

of particulate

and hydrocarbons.

available

data

in

is

insufficient

matter
that

data

standard.

can reduce

to

the emission

1 kg particulate

per

Technological
affect

matter

trends

of higher

catalysts

and/or
emitted

additives.

reducing

catalyst

quantity

of

The particulate

sists

primarily

Additional

of

standard

coke

burned

matter

of catalyst

particulate

matter

off

fines

quantity

include

and new

of particulate
in the quantity

in catalyst

of

flow rates,

This reduction

allowable

emissions

does

are based

catalyst.

from

a FCC unit

produced

is the result

6-1

to signifi-

These trends

emissions.

the

emitted

burn-off.

and regenerators,

because

effec-

a change in the

standard.

by a reduction

and carbon

matter

kg of coke

and a reduction

present

have been

do not appear

The actual

be affected

the present

to justify

reactors

coke formed on the catalyst

on the

consists

to the

technologies

1,000

matter

temperature

will

a change

in the industry

the particulate

use

not affect

carbon

of environmental,

of particulate

NSPS of

thereby

matter,

effects.

New control

degree

matter

light

support

but not to a sufficient

the

revisions

The analysis

and process

tively,

cantly

of possible

Matter

particulate
developed

TO THE STANDARD

the analysis

technology,

Particulate

There

the

dioxide,

an examination

6.1

will

REVLSIONS

regenerator

in the first
of ch~mical

stage

con-

cyclone.

reactions

in

'"]

the flue gas whichresult in the formationof condensablesulfates.

Theparticles rangein size from05 micronto 60 micronsin diameter

14i

withas much
as 86percentof theseparticlesgreaterthan10microns
in diameter (Bal -t, 1976). As a result, a numberof control tech-

jl
lid

rl

aolugies
areluit.ble
iorfeduciog
fheemisriao
level,bufprese.r
data showthat electrostatic precipitators are the best demonstrated
control technologyconsideringcost for minimizingthe final emission

level.Only
filtersareasefficient
at removing
small
particlep
as
electrostatic precipitators Wetscrubbers,whichhavethe potential
for efficient small particle removal, also have the addedadvantage

(froman environmental
viewpoint)of removingsulfur compounds.
The measurementof particulate matter requires the use of

ReferenceMethod5 or its equivalent It has been recognizedin

the past that condensable

particulatematterwill collect in the
impingersof the Method5 samplingtrain. This material is not
included in the reportable particulate matter catch. It wasalso

recognizedthat condensable
particles were'beingcollectedin the
samplingprobeandon the filter (EPA,1975). Theseparticles are
;

reportable as particulate matter~

Most of these

condensable

parti-

cles are believed to be sulfuric acid mist. a highly hygroscopic

material, and other sulfates.

Becauseof this, it is difficult to

actually be assured of the quantity of catalyst fines, condensable

particles, andmoisturebeingmeasuredAt present,all this material

is,

by definition,

particulate

matter~

6-2

There are no CDS opacity

there

is

no requirement

same time

emission
result

is

the

of opacity

be

This

attained

in

matter

standard

continuously

during

increase
could

the

(EPA,

period

be maintained

high

efficiency

erosion,

This

accessable

because

for

dependent
ciency

change

is

ticles

in

inlet

tribution
reduce

the

of the
the

or longer

the

stream.

Efficient

the

size

efficiency.

6-3

tend

prone
is

separator

preceding

it.

distribution

Separator

to

but upstream

regenerator,

inlet

of an additional

to be less

cyclones

separator

without

emissions

use

the

nor-

formainte-

particulate
the

than

are

emissions

of

cyclones

to

separator

the

efficiency

of the

in

systems

Fnaccessable

reported
to

due primarily

particles

that

level
systems.

to the regenerator
is

The

efficiency

the

through

external

maintenance.

on the

level

separator
is

would

relationship

regenerator

of erosion,

external

it

mass

at a higher

that

are

possible

a lower

separator

and,

is

on the

up to two years

cyclones

It

at

precipitator.

fact

and because

1973b).

the

but the reverse

was set

of the

The internal

to require

data

FCC unit

for

at

FCC regenerators.

installed

operated

nance

fore

newly

that

and opacity

no reason

significant
from

The fact

emissions

is measured,

emissions

in recognition

maj or shutdown.

the

of

was done

mally

is

opacity

availability

The particulate
can

mass

There

whenever

and mass

to conrment on.

record

a shortcoming.

testing
in

to

data

change

to

more
is

This
of the

the

stream
efficiencies

size

effipardis-

and thererange

of

from approximately 70 percent

t,

.,,,

in units with highly

90 percent

respectively

(Krueding,

efficient i"ternal cyclonesto pOOrcyclones,

1975)

6. 2

Carbon

Monoxiae

TheNSPS
forcarbon
monoxide
canbemetbytheuseofa waste

hearholler
which
noronlycontrols
emissions
~Utrecovers
the
heatvalreoftheaxida~ian
reacfion
oicarboo
monaxide
tocarbon
d~oxide
meOrher
commonly
used
central
technology
is combusrian
ofthecarbon
monoxide
in theregenerator
itself Theadvantages
of in situ

regeneration

,,,:

increasedyields of usefulproducts,

decreasedemissionsof particulate matter,

and recovery of waste heat

the carbon

in anenergyexpanderThereis noCDS
dataon
in
emissions
froma regeneratorusingregenerator
carbon

situ

monoxide

combustion Of

monoxide

Inthepast,themetallurgy
Oftheregenerator
"d cylones
WaS
FCC units

a limitingfactor whichdetermined
those

capable of
The

recent

operating
withhightemperature
in "itucombustion
and additives
development
of carbon
monoxide
oxidation
catalysts
permitted "ny units to

.t

least

has

and often completely,

partially,

without resorting to high

oxidizecarbonmonoxide
in the regenerator
temperatures

Little

data are available

On

carbonmonoxide
fromFCCunit regenerators
~tors

An additional

advantage

the emission level of

using CO oxidation

prO'

of using the Oxidation promoter

,ye,conventional
hightemperature
regeneration
iSthatthe
6-4

oxidation

reaction

is reduced,
will

remains

in the dense bed,

and presumably erosion

be reduced.
although

6. 3

Dioxide

Sulfur

and particulate

There is no data

conclusion,

it

is

the cyclone

as yet

temperature

matter emissions

to substantiate

the last

reasonable.

The present NSPSfor sulfur dioxide limits the concentration of

hydrogen sulfide in fuel gas burned in a petroleum refinery to 230

mgH2S/dscmof fuel gas. There is provision for the refinery
owner/operator to reduce sulfur dioxide emissions in flue gas
instead

of hydrogen sulfide

in fuel gas.

available

at the EPA Regional offices

presently

reducing the concentration

substantially

below the present

sulfur

content

indicate

the

are

of H2S in fuel gas to levels

was being reduced (efficiency

nor how the H2S concentration

of

that refineries

NSPS. There were no data to indicate

by what amount the H2S concentration

of the controls)

The CDS data that were

related

to the

feedstock.

According to Gary and Handwerk (1975), amine gas treating

units

usually reduce sulfur concentrations to less than 5.72 mg/dscm. The

concentration

of H2S in treated

fuel gas reported

in the CDS files

ranges from less than 7 mg/dscm to 229 mg/dscm (Watson et al.,

Although the compliance test
above

the concentration

measurements are still

concentration

allowed

data show concentrations

reported

in Gary and Handwerk,

substantially
by

the

NSPS.

6-5

1978).

significantly
most of these

below the 230 mg/dscm maximum

P1
II
r

Presently,thereis noNSPS
for sulfurdioxideemissions
from
the fluid catalytic cracker regeneratornor fromthe regenerator

B/

,,,,,,,,.....,,,,~~~...
mo
PCC
unir
r~$inPr~or
nll~ion.
or
2.3 x 108 to 3.9 x 108 kg/yr based

lliI

sulfur
oxides
areIs;-imated
at

III

Inaddition,
thereareadditional
sulfur
oxide
emissions
from
the

oncurrentFCC
capacityandemission
factorsfromthe EPA(1973).

regenerator
wasteheatboilerdueto theuseof auxiliary
fuel. The

II

actualquantity
ofemissions
depends
onthesulfu+
content
ofthe
auxiliarygaseous,
liquid,or solidfuel. Evenif fuelgasis used
as the auxiliaryfuel, there are no requirements
to controlSOxas

the boilerhasbeenexempted
fromthe sulfurdioxidestandardfor
fuel

gas combustion

devices.

State air pollution standards (1976) for SO, fromnewsource

FCCunit regeneratorsrangefrom440ppmto 2,000ppmin the flue gas.

However,
the actualachievable
emission
rate is dependent
onfeed-

stock,feedstock
sulfurcontent,andotherprocessvariablesIf
the feedstockis lowin asphaltenes,hydrodesulfurization
mayhave
the capabilityto reducethe sulfur oxideemissionrate. Process

variablessuchas hightemperature
regeneration
andthe useof SO,

recyclecatalystsmayalsobecapable
of reducing
thelevelof SOx
emittedfromthe regenerator.Dataare not availableto specifythe
actual

levels

of these

emissions

6-6

6.4

hydrocarbons
The emission

addressed
bons

in

the

because

hazards

bons

the

present

of

the

are

FCC unit
which

are

nuclear

of smog.

6-1

lists

and

are

flue

gas

Table

stream.

(PNA's)

The most

hazardous

The

concentration

bon monoxide boiler

(Arthur

D. Little,

concentration
regeneration
moting

1976).

the

case

with

known

to

concern

potential

flue

an uncon-

the
be

hydrocar-

present

are

in

the

poly-

carcinogenic

gas

is

benzo-a-

of 0.218 kg BAP/1,000 barrels

effectively

be

There

are

no data

gas from high

of regenerators

reduced

catalysts.

6-7

in

of
a car-

of feed

to determine

temperature

using

health

hazardous

from

to 1.41 x 10'5 kg BAP/1,000 barrels

Inc.,

in

their

gas

some of

regenerator

BAP can

of BBP in the flue

nor

of

PNA in

of

compounds

flue

Of particular

because

abundant

the

not

in hydrocar-

A number of potentially

regenerator.
be

is

interest

these

in

to

regenerators

a great

of many of

pyrene (BAP) with a concentration

feed.

is

known to be present

aromatics

effects.

FCC unit

There

relationship

known

regenerator

from

NSPS.

and the formation

hydrocarbons
trolled

of hydrocarbons

the

tin situ)

CO oxidation

pro-

::

TABLE 6-1

HIIZARWUS
HyDROChRBONS
~ITTED
FROM
FCC
UNIT
BeGBNERATORS
Concentration

r/

Hydrocarbons

(ppm)
3-130

Aldehydes las H2CO)

0.19

0.94

Cyanides las HCN)

2,070a

Il(i

Anthracene

40 - 28,000a

Pyrenes

.t

Benzo (ghi)

15 - 424a

perylenes

4 -

(I

Benzo

(a)

pyrene

Benzo

(e)

pyre"e

460a

11 - 3,600a
400,000
Phenanthrenes

a Micrograms
per barrel of oil charged
Source: Bombaughet al.,

1976.

6-8

7.0

CONCLUSIONS

7.1

Particulate

Matter

The available
NSPS.

the

due

current

standard

The
sions

remains

Reference
to

train

regenerator

There
finding

for

in situ

for

and operating

total

of calcu-

corrected

measuring

the

procedures.

particulate

because

amount

of

that

it

is

CO oxidation

is
situ

monoxide

the

The

matter

emis-

temperature

condensable

less

of

particles

the

present

not

to

practical

than

no

compliance

based

carbon

substantiate

on

the

use

monoxide

in the

control

CO emissions

to

The recent

adventand

additives
test

may have
data

were

altered

found

to

Sulfur

original

less

than

increased

use

that

original

substantiate

Dioxide

A number

of conclusions

regarding

7-1

the

present

of

boiler.

this.

7. 3

in

carbon

any change

to

regeneration.
and

was

This method of controlling

effective

data

catalysts

although

emissions

combustion.

insufficient

500 ppm by in

finding

the

matter.

carbon

emissions

are

high

Monoxide
NSPS

monoxide

5 for

the

particulate

Carbon

catalysts

preseui

reduced

The method

already

controversial

affects

measured

The

be

has

the

separators,
have

emitted.

to

valid.

Method

continues

sampling

in

efficiency

new catalysts

emissions

to changes

any changes

as high

matter

allowable

reduction

support

and

of particulate

lating

7. 2

such

regeneration,

quantity

of

do not

New technologies

temperature

the

data

NSPS for

sulfur

dioxide
havebeendiscussed
previously,
namely:

standard
is difficult
monitoring
method.

to ensure

Compliance with the p~esent

without

a continuous

Compliance test data

allowable
~~~centration

indicates

that a reduction in the

hydrogen sulfide in fuel gas is

of

po ssible

The present
excluded

for fuel gas combustion devices has

standard

waste-heatboilers

regenerator

even though they may,

in fact, generateand emit SOxwhenusing fuel gas as an

auxiliary

fuel.

Although

standard

a separate

promulgated

for regenerator

for particulate

matter

was

waste heat boilers using liquid

applies to the SO, genstandard

used. This should be examined if

or solid
fossil
fuel,
no
erated
when these
fuels
are

fuel gas combustion devices

the SOxstandard is revised forfor FCC
unit regeneratorsor a standard

The FCC unit

is developed

emits significant quantities of sul-

regenerator

fur oxides which are presently

uncontrolled.

for the reduction of sulfur dioxide emissionsfrom

industries exist and maybe applicable to FCCregener-

ogies
other

there are FCCregenerators with SOx

At least ten states have a sulfur oxide

ators,
and, in fact,
emission
controls

emission limit for FCC regenerators

and new sources and may be a source

bility

of SO, control

Little
content

is known of
of feedstocks

the regenerator
higher
and

well

7.4

Control technol-

sulfur

this

will

as on the

of data

to existing

on the

applica-

devices.

the actual effect of an increased sulfur

on

the emission of sulfur oxides from

are being

Refineries
content
have

which apply

an

ability

forced

to process

feed due to shortages of domesticcrude

effect on the final emission level as
to

control

the

emissions

Hydrocarbons

Thereis not enough

known
aboutthe emissionof hydrocarbons

fromFGC
units to justify settinga standardThepresentdata
however
indicatethat: the uncontrolled
emissions
are significant,
they

depend on the process,

effects,

and because of potential adverse health

they may require control.

7-2

8. O

RECOMMENDATIONS

The
for

following

recommendations

particulate

matter,

Particulate

Matter

carbon

are

made

monoxide,

regarding

sulfur

the

NSPS

dioxide,

and

hydro-

carbons.

8.

Do not change
coke burn-off

Reevaluate
matter

8.

Carbon

the

8. 3

5 for

particulate

that

opacity

be measured

when mass

loading

tests

Konoxide

Collect

data

to

from

without

Reevaluate
findings

Sulfur

Method

kg

made.

emissions
and

Reference

1.0 kg/1,000

Require
are

the present
standard
of
and 30 percent
opacity.

ascertain

high

the

the

level

temperature

use

of

tin

CO oxidation

the carbon
monoxide
from the above
research.

of

carbon

situ)

monoxide

regenerators

catalysts

standard

in

and
light

with

additives.
of

the

Dioxide

Qlange the definition

of a fuel gas combustion
device
to include
the regenerator
incinerator-waste
heat boiler
deleting
the exemption.
Develop

a continuous

monitoring

method

for

by

hydrogen

sulfide.

Reevaluate
increased

the

present

sulfur

hydrogen
sulfide
data on achievable

standard

in light
on

the

effect

of

in

gas and of current

compliance
of hydrogen
sulfide
in fuel

fuel
levels

feedstock

of the

content

of an

concentration

of

test
gas.

Investigate
FCC unit
regenerator
sulfur
oxide control
technology,
including
cost,
performance,
applicability,
effect
of
feed stocks,
etc.
Subject
to the findings
of such an'investigation,
develop
a standard
for sulfur
dioxide
emissions
from
FCC unit
regenerators.

8-1

B
8. 4 Hydrocarbons

Evaluate

the effect

ers, high
combustion

temperature
catalysts

of:

regeneration,
co~entional

COboil-

regeneration,
a"d regeneration
withCO

and additives on the emissionof hydro-

carbons fr-- PCCunit regenerators~

Assess
from

the need for

FCC unit

the regulation of hydrocarbon

emissions

regenerators

based on results from the above

research

8-2

11

9.0

REFERENCES

American
Petroleum
Institute,
1978.
Wastes.
Volume on Atmospheric
Arthur

D. Little,

Inc.,

1976.

Manual on Disposal
of Refinery
Emissions.
Washington,
D.C.

Screening

Study

to Determine

for SOx and Hydrocarbon NSPS for FCC Regenerators.

Springfield,

VA.

Balfoort,
J.P.,
Flue Gas.
'Barbier,

PB-275

1977.

Processing

N~IS,

162.

1976.
Improved Hot~as
Hydrocarbon Processing

J.C.,

Need

Expanders for Cat Cracker

55(3):141-143.

Save Energy When Making Gasoline.

Hydrocarbon

56(9):85-96,

Bombaugh, K.J., E.C. Cavanaugh, J.C. Dickerman, S.L. Rail, and T.P.
Nelson, 1976.
Sampling and Analytical
Strategies
for Compounds
in Petroleum Refinery
Streams, Volumes 1 and 2. Radian Corporation.
~TIS, Springfield,
VA. W-251 744 and PB -251 745.
Braun,

S.S.,
Gas

C.F.

1973.

Journal

Braun

C Company,

Cracking

Cantrell,

Power Recovery

Units.

A.,

Pays Off at Shell

Oil.

Oil and

71(21):128-134.

1975.

1976.

Power Recovery

Alhambra,

for

Fluid

Catalytic

CA.

Annual Refinery

Survey.

Oil and Gas Journal

Annual Refining

Survey.

Oil and Gas Journal

73(14):96-118.

Cantrell,

A.,

1978.

76(12):108-142.

Dickerman,

J.C.,

Industrial
Petroleum
Springfield,

Gary,

T.D. Raye,

J.D.

J.H. and G.E. Handwerk,

and Economics.
Chemical
L.F.

Colley,

and R.H. Parsons,

Process
Profiles
for Environmental
Use:
Refining
Industry.
Radian Corporarion.
Vet PB-273 649.

Albright,

R.N.

1975.
Petroleum Refining,
Processing
and Engineering

Maddox,

Huddle,
J.,
1978.
Personal
Company and K Barrett,

and J.J.

McKetta,

1977.

Chapter
KIIIS,

3.

Technology
Volume 5.

ed.

communication.
J Huddle,
AMOCOOil
The Metrek Division
of The KITP,E

Corporation.

Hydrocarbon
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Feb.

1978.

World-Wide

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9-1

BPI Construction

Boxscore,

a
Krueding,
A.P., 1975. CatCrackerPower
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ChemicalEngineeringProgress 71(10):56-61.

Laster,

L.L.,

1973.

Atmospheric

Emissions from the Petroleum

NationalEnvironmental
ResearchCenter,Research

Industry.

Triangle

Par'-

ET~IS,Springfield, VA PB-225040.

NC.

Modern FCC Units

Incorporate

Murphy, J.R. and M. Soudek, Oil

1977.
and Gas Journal 75(3):70-76
Many Design Advances~
Nader,

J~

Personal communication.US Environmental

1978.

Protection

Research Triangle Park, and K, Barrett,

Agency,

The Metrek Division of The MITRECorporation

OilandGasJournal,1977.MobilPlansRecovery
fromFCC
Unit'Oil
and Gas Journal

75(9):66,

Ritter, J.J. Blazek,andJ.A. Montgomery,

1976.

Rheaume,
L,
R.E.
New FCC Catalysts
Grace

Cut Energyand Increase Activity W.R.

Oil and Gas Journal 74(20):103-110.

~ Company.

Rheaume, L~ R,E, Ritter,

J.J.

Blazek, and J,A, Montgomery,1976a.

Oxidation Catalysts Get Commercial

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W.R. Grace & Company

Oil and Gas Journal 74(21):

66-70,

Protection Agency,1973. Compilationof Air

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Environmental

U.S.

Environmental
ProtectionAgency.
1973a.Background
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Pollutant
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NewSourcePerformanceStandards: Asphalt Concrete

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Plants,
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New

Volume

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PerformanceStandards: Asphalt ConcretePlants,

Storage Vessels, SecondaryLead Smelters
Refineries,

Refineries,
Steel
Plants,

Promulgated
Park, North
U.S.

SewageTreatment Plants.

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Petroleum
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and

Brass and Bronze Ingot Production

Office Plants,
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Environmental

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to

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9-2

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Environmental

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Test Report

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Personal communication
between E.L. Keitz, The Metrek Division
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Vasalos, I.A., E.R. Strong, C.K.R. Hsieh, G.J. D'Souza, 1977. New
Cracking Process Controls FCCUSO,. Oil and Gas Journal 75(26):
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~flTR-7772.

McLean, VA. (Draft)

9-3

Metrek

Regional
Division

APPENDIX

REPORTED

UNITS

FLUID

AT

CATALYTIC

PETROLEUM

~RACR~I~NG

REFINERIES

APPWDIX
BZPORTED

PCC

UNITS

ii

AT PFPBOLEUN

BeFZNEBfES

PCC Bapacitp

EPARegion
Begion

Company/City

(W/sd)

1975a

1978b

Change*

125
40
22

155
40
22

10
O

187

197

10

I:

Connecticut

None

reported

~oine
Lkssachuaetts

Nev BaPlpshFre
abode

Island

Vermont
Subtotal

8egion

II:

Nev Jersey

EHan, Linden
Tezaco, UestvFlle
Ashland,
North Too~avanda

Nev YorL

Subtotal:

Begion

III:

Delracare

Cetty,

Karpland

None

Permeylvania

DeZlruare City

62

62

BP, Llarcue E~oolr

40

48

Gulf, Ph~l~A~~phia
SIIOI ILLtCUB BooJC
Ihited,
Varren

80
75
r0

84.6
75
11.5

Virginia

~L~Dco,Yorlrtow

27

28

Vest Virginia

None reported
309.1

15.1

Subtotal:

r~ncreasel(decraasa)
Change

in

reported

294

8
~ 4.6
0
1.5

in PCC capacity

ounerabip

Igeportedin L~led.~ld calculaeed

(~/cd
Sources

- tbouaand barrels

day, ~led

aCantreli,
Csntrell,

per calendar

1975.
1978.

A-i

- thousand barrels

per stream day)

REPORTED
FCCUNITS
ATPETROLEUM
REFINERIES
FCC CapacitY

Compan_y~l'_

EPA Region
Region

(Hb/sd)

1975a 19786

IV:
None reported

Alabama

Florida

Georgia

Ashland, Catlettsburg
Ashland, Louisville

Kentucky

Chevron,

Mississippi

Pascagoula

Standard
of Kentucky,
Pascagoula

North Carolina
South

54

54

O
(0.5)

10
56

10.5

56 T

56

(56)t

Nonereported

Carolina

Tennessee
Subtotal

Region

120.5

120

(0.5)

V:

Illinois

38

Amoco, WoodRiver

Clark, Blue Island

Clark, Hartford
~iarathon, Robison
Mobil, Joliet
Shell, WoodRiver
Texaco, Lavrenceville

Texaco,
Lockport
Union
of CA, Lemonf
Indiana

Amoco, Whiting
Atlantic

Richfield,

24
26
36.5
66
94
31
30

54

118

48

East Chicago

Enerey Coop, East Chicago

38

26

26

36.5

26
O
3

30

140

22

55
48

Indiana FarmBureau,
Mt. Vernon
RockIsland, Indianapolis

6.1
15

17

Iowa

Nonereported

25.5

Marathon, Detroit

21.5

Michigan

ninnesara
Wisconsin

Total Leonard, Alms

Total petroleum, Alma
Continental. Wrenshall
Koch, Pine Bend
Koch, RosemDnt

Northvestern, St Paul Park

MurphY,Superior
Subtotal

12

9.5

24

21
9,7
684.3

92
94
34

6.3

16
9.5
45
22
9.7

770.5

(48! t

48 t
0.2

4
(12)

16t
0

(24~t
45
1
O

86.2

*Incre~s~e~/~(decrease)i" FCCcapacity
tChange in ownership

IReported
in Hblcd,
Hblsdcalculated
barrels
per calendar
(Mb/cd-

thousand

day,

Mblsd- thousandbarrels per streamday)

Sources:

aCantrell,

1975.

liCantrell,

1978.

A-

REPOI~ED PCC IMITS A~ PSTBDLE1M PEPIHEBIES

PCC

EPh Begion
Regioo.

Compan~Ci~

~75'

1978"

Change"

VI:

hrlcansas

lion OI1 Co.. Eldorado

Louisiana

Cities

Service,

Lalre Charles

Ermn, Bacon Bouge

Good hope Bef., Goodhope
Culf. Belie Cbasee
~urphy, ~eraur
Shell. Norco
fenneca,

Chainette

reraco, Convent
Hev ~erico

Shell

OLkha~a

OF1, Cfni..

16)
15
78
10.5
100

169
17
78
10.5
100

6
2
0
0
0

22

22

70

70

~sco. Cyril
Cbalplin, Enid

6
19.5

6.7
19

Continental,

44

44

Tsraco,

Yest ~ulsa

Vidrers, ~LrdDre
~Lpcrican, port kthur
dnoco, Teras City
~Lrlantic

gichfield,

~hareet.

Boctston

houston

Inecrpatiollal.

Chevron, El Paso
Coastal

Statea,
Pig

Spring

ho~o. Central,

houston

E~m. 8~9 tovn

Gulf, port drthur
La Cloria,

18

0.7

(0.5)
0

1
11.5
25
30
18

21.5
32
167

7
0
(7)
0
0
0

8.5
2

32

69

74

10

54

44

24

37.5

13.5

22

22

Corpus

~hr2~~i
Coaden,

11.5
7
25
3)s
13
30
135

Cbanplin, Corpus Chriati

7.2

Ponea City

15

125

7.2

hudson, Gushing
Icrr-~cCse. Yynnevood
Ilddand, QuhLng
Sm, I~unc~n
Suit. Tuka
Terse

15

125

~lcr

19

19

24

24

43

43

124
120

135
120

Karathon, 2eras Ctiy

28.5

30

10

Kobll,

80

90

10

55
30

56
34

1
4

70
10.5

70
10.5

0
0

12

2.5

27

0
0
0
0

~e~u~D~r

Phillips.
Phillips,
Shell.
Shell.

Borger
Svceny

Deer ParL
Odaasa

baurbvartcm,

Corpus

~rLti

Sonrid~.
,,, ,,,,
Site. Corpus Qristi
~upeo. Ibsrillo
rcaeo,
hi Paao
Psneo.
Port Lrthur
raru
City,'Leraa
City
mion
Pnioa

of Calif.,
of Calif.,

Yinston,

Icdc~lnd
~u~ont

10

1l

9.5

20
27

"

Port Vorth

Subtotal:

1.5

3.4
1933.6

2080.8

'~P
O
147.2

LIncreaael(defrsaK)in PCCcapacity
Change

in o~e~hie

Igeported in ~lcd. ~Id calculated

(~Blcd- thousandbarrala per calendar day, I(bld - thousandbrrCL per atrean day)
Sourcea

Canrrall.

1975.

Clntrell,

1978.

A-3

REPORTED
FCCUNITS
ATpETROLEUI3
REFIE~T~RIES
FCC CaoacitY

EPA
Region
RegionVII:
Kansas

1975a

c~e~rl~FYL
Americanpetroleum, El
Dorado

11
9.2

Getty, El Dorado
National Coop, HcPherson
pester, El Dorado

20

APCO,
ArkansasCity
CRA,Coffeyville
CRA,Philllp
Derby,Wichita

14.5
7
10.8

phi!.lips, KansasCity
Skelly, El Dorado

fllasouri
Nebraska

Gulf, Cleves
Standard of Ohio, Lima
of Ohio, Toledo
Standard
Sun of pennsylvania, Toledo
Subtotal:

Asamera, Commerce City

Continental,
Commerce City

TheRefineryCorp.,

Hontana
North

Dakota

SouthDakota
Utah

Nonereported
Amoco,Salt take City

Chevron, Salt Lake City

wjor.Roos~velf
plateau,

Roosevelt

Amoco, Gasper

Wyoming

Huskyl Cheyenne
Rusky, Cody
Pasco, Sinclair
Sinclair,
Texaco,

Sinclair

Gasper

*Increasel(decrease)

O
0

37.7

07

55

50

50

383.4

373.3

(10.1)

14

15

7.6

19

12
15

19.2
1.8

(7.6)t
15
1
0.2

23

23

17

18

11

10

5
9.5

10

3.3
17.7
7

169.4

Subtotal:

24.5

18

1.8

Great Falls

41
2.4

37
55

Exxon, Billings
Amoco, Mandan

Ot

18

10.5
14

Phillips~

0
11'

(0.2)

Commerce
City
Cenex, Laurel

Continental,
Billings

15
1.5
0
17t

19.8

Region VIII:
Colorado

0.4

(31)

20

Gulf , roledo

9.6

16
8.5
10.8
17
32

24.5

Ashland, Canton

Ohio

(Il)t

11

(12.4

CRA,Scotts Bluff

Chang~_*

20

32
31

A~ca.Sugar
Crrelt

(Mblsd)

1~

5.2 (:IZ
9.4

10

3.3
17.7
_7_

174.6

(0.1)
O

O
(177!tt
17.7
O

52

in FCC capacity

iChange in ownership

IReporredin Wlcd, Hblsdcalculated day,Hb/sd(Hblcd- thousandbarrels per calendar

Sources:

aCantrell,

1975.

bCantrell, 1978.

A-4

thousand
barrelsperstreamday)

REPORTEDFCC UNITS AT PEFROLEUHREFINERIES

EPARegion
Region

FCC

Company/City

lX:

Arizona
California

None reported
Atlantic Richfield,
Carson
Chevron,

57
El Segundo

Chevron, Richmond
Exxon,

Benecia

47

55

55
1

Gulf, Santa Fe Springs

HobFL, Torrance

13.5
56

13.5
60

O
4

Phillips,

47

Avon
Oil,

Sante

Tosco Corp.,
Union Oil

11
46
35

28 B

Lion Oil, Avon

of Calif.,

Angeles

11.5
46
35

0.5
O
O

47

47t

28 g

Los

Chevron,BarbersPoint
Standard

(47)t'

Fe

Texaco, Vilmington

45

45

19

19t

of Calif.,

Barbers Point
None reported

Nevada

(1)

47
46

Springs
Shell Oil, Hartinez
Shell Oil, Wilmington

Hawaii

56

45

Poverine

Subtotal:
Region

(Mb/sd)

1975a

14.1
397.6

(14.1)t
509

111.4

X:

Alaska

None reported

Idaho

Oregon

Washington

Shell, Anacortes

Texaco, Anacortes
Subtotal:

GRAND TOTAL

36

36

27

30

63

66

4232.8

4600.3

3
367.5

*Increasel(decrease) in FCCcapacity
Change in ownership
Reported

in Hb/cd,

Hb/sd

calculated

(w/ca- ehausand
barrel.per calendarday,~/sd.- thousand
barrelsperstreamday)
Sources:

BCaatrell, 1975.
Cantrell,

1978.

A-5

TECHNICAL

REPORT

DATA

I~lc~sereed Inshucrionson the reversebe/we completing~

i. REPORT

NO.

RECIPIENT'S

2.

ACCESSION

NO.

EPA-450/3-79-008
TITLE

AND

REPORT

SVBTlTLE

A Reviewof Standards of Performance for New

Stationary

January 1979

Sources - Petroleum Refineries

16.PERFORMING
ORGANIZATION
CODE
PERFORMING

7. AUTHOR(S)

Kris

Barrett

.PERFORMING

and Alan Goldfarb

ORGANIZATION

NAME

AND

to.

ADDRESS

NO.

PROGRAM

ELEMENT

NO.

68-02-2526

tZ. SPONSORINGAGENCYNAMEAND ADDRESS

(13. TYPE OF REPORT AND PERIOD COVERED

DAA for Air Qu~T.ity Planning and Standards

Office of Air, Noise, and Radiation
U. S. Environmental
Protection
Agency

Research Triangle

REPORT

;I.CoNTRACT/GRANT
NO.

Me Lean, VA 22102

5. SUPPLEMENTARY

ORGANIZATION

MTR-7825

Metrek Division
of the MITRE Corporation
1820 Dolley Madison Boulevard

t6.

DATE

t4.

Park, NC 27711

SPONSORING

AGENCY

CODE

EPA 200/04

NOTES

ABSTRACT

This report reviews the current Standards of Performance for NewStationary

Sources:

Subpart J - Petroleum Refineries.

It includes

a summary of the

current standards, the status of current applicable control technology, and

the ability of refineries to meet the current standards. Compliance test
results are analyzed and recommendations are made for possible modifications
and additions to the standard, including future.studies
needed for unresolved
issues.

1-.

I
7.

KEY WORDS AND DOCUMENT ANALYSIS

DESCRIPTORS

ts. DISTRIBUTION

Release

b.lDENTIFIERSIOPEN ENDEDTERMS

STATE MENT

19. SECURITY CLASS (ThL ReporrJ

Unclassified
20. SECURITYCLASS(ThiJpoge)

Unlimited

Unclassified
EPI

Form 2220-1

(Rc*. 4-77)

PREVIOVS

EDITION

IS OBSOLETE

c. COSATI Field/Group

i 21. NO. OF PAG ES

83
22. PRICE