PB82-237041
Source Test and Evaluation Report
Alcohol Facility for Gasohol Production
Radian Corp.
McLean , VA
Prepared for
Industrial Environmental Research Lab.
Cincinnati, OH
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
BJPFlCt

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EPA 600/7-82-018'
April 1982
PB62 -23 7 0 4 1
SOURCE TEST AND
EVALUATION REPORT:
ALCOHOL FACILITY FOR
GASOHOL PRODUCTION
Final Report
by
R. M. Scarberry and M. P. Papai
Radian Corporation
Suite 600, Lancaster Building
7927 Jones Branch Drive
McLean, Virginia 22102
Under EPA Contract No. 68-03-2667
Project Officer
Paul E. Mills
Technical Project Monitor
Thomas J. Powers, III
THE UNITED STATES
ENVIRONMENTAL PROTECTION AGENCY
26 WEST ST. CLAIR STREET
CINCINNATI, OHIO 45268

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1 REPORT NO 2.
EPA-600/7-82-018 ORD Report
3 RECIPIENT'S ACCESSION NO.
PM7 2 3 7 0 4 1
4 TITLE AND SUBTITLE
Source Test and Evaluation Report: Alcohol Synthesis
Facility for Gasohol Production
5 REPORT DATE
ADril 1982
6 PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
R.M. Scartarry & M.P. Papai
8 PERFORMING ORGANIZATION REPORT NO
9 PERFORMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
Suite 600, Lancaster Building
7927 Jones Branch Drive
McLean, Virginia 22102
10 PROGRAM ELEMENT NO
C2JN1E
11 CONTRACT/GRANT NO
68-03-2667
12 SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Abency
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
13 TYPE OF REPORT AND PERIOD COVERED
Final; 10/78 - 2/80
14 SPONSORING AGENCY CODE
EPA 600/12
15 SUPPLEMENTARY NOTES
16 ABSTRACT
This study defines the requirements for environmental sampling and analysis of
alcohol-producing facilities capable of supporting a Gasohol industry and applies
these requirements to the environmental characterization of an alcohol plant. This
document includes a conceptual design of a grain alcohol plant using a coal-fired
boiler that is projected to be typical of future plants which will support a Gasohol
industry. Environmental control options are also discussed based on a comparison of
alcohol plant stream compositions with environmental regulations. The results of
this study provide preliminary information on the environmental consequences of
large-scale fermentation ethanol plants which will provide alcohol for Gasohol.
17 KEY WORDS AND DOCUMENT ANALYSIS
a DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
c COSATi Field/Group



18 DISTRIBUTION STATEMENT
Release to Public
19 SECURITY pL^SS (This Report)
Unclassified
21 NO OF PAGES
197
20 SECURITY CLASS (This page)
Unclassified
22 PRICE
EPA Form 2220-1 (Rev. 4-77) previous eoition is obsolete

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DISCLAIMER
This report has been reviewed by the Industrial Environmen-
tal Research Laboratory, U.S. Environmental Protection Agency,
and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the U.S.
Environmental Protection Agency, nor does mention of trade names
or commercial products constitute endorsement or recommendation
for use.
ii

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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our envi-
ronment and even on our health often require that new and in-
creasingly more efficient pollution control methods be used. The
Industrial Environmental Research Laboratory - Cincinnati (IERL-
Ci) assists in developing and demonstrating new and improved
methodologies that will meet these needs both efficiently and
economically.
This document was prepared to provide IERL-Ci with informa-
tion concerning - the requirements for the environmental character-
ization of an alcohol plant. It should prove useful as a guide
in future sampling efforts conducted for the alcohol industry.
In addition, this study was conducted to furnish IERL-Ci with en-
vironmental data from a commercial facility currently providing
anhydrous ethanol for Gasohol. This information can be used to
determine the environmental impacts from large-scale alcohol
plants. Further information concerning this subject can be ob-
tained from Robert Mournighan of the Advanced Energy Systems.
Branch, Energy Pollution Control Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii

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ABSTRACT
This study defines the requirements for environmental sam-
pling and analysis of alcohol-producing facilities capable of
supporting a Gasohol industry and applies these requirements to
the environmental characterization of an alcohol plant. This
document includes a conceptual design of a grain alcohol plant
using a coal-fired boiler that is projected to be typical of
future plants which will support a Gasohol industry.
Environmental control options are also discussed based on a
comparison of alcohol plant stream compositions with
environmental regulations. _The results of this_ study provide
preliminary information on the environmental consequences of
large-scale fermentation ethanol plants which will provide
alcohol for Gasohol.
This study was conducted by Radian Corporation, McLean,
Virginia, under the direction of Mr. Gilbert J. Ogle, Program-
Manager. The program was carried out under EPA Contract No.
68-03-2667.
iv

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CONTENTS
Foreword			iii
Abstract 		v
Figures	vii
Tables	viii
Abbreviations 			xi
Acknowledgments 	 xii
1.	Introduction 		1
Objective 		1
Background 		1
Approach . . -. . - . . - . . - . ;	2
2.	Conclusions and Analytical Results of an Alcohol
Plant Environmental Characterization ........	4
Conclusions and recommendations 	 4
Results 		8
3.	Alcohol Process Evaluations/Conceptual Design ....	26
Fermentation ethanol production 		26
Conceptual design of an alcohol fuel plant ... 28
4.	Review of Environmental Regulations 		54
Methodology		54
Air regulations		57
Water regulations		59
Solid wastes regulations 		66
5.	Control Technology Requirements 		68
Air emissions control			68
Wastewater treatment 		76
6.	Sampling and Analytical Requirements for an Alcohol
Facility		82
Characterization objectives 		82
Process analysis 		83
Sampling procedures 		87
Analytical methods . 			89
Data evaluation procedures 		91
7.	Test Plan		97
Objectives and scope		97
Process analyses 		97
Sampling procedures 		119
Analytical techniques			124
Data evaluation	12 7
8.	Sampling and Analysis of an Alcohol Facility ....	129
v

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Bibliography			134
Appendices
A.	Flow diagrams and mass balances for selected
alcohol plants 	 149
B.	Supporting data for Section 3 environmental
regulations	167
vi

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FIGURES
Number	Page
1	Flow diagram for an alcohol facility		2 7
2	Flow diagram for conceptual design 		33
3	Steam and power generation 		35
4	Wastewater treatment facility 		41
5	Alcohol - plant .flow diagram-.—. . . . .	99
6	Grain preparation 		10 7
7	Cooking and cooling . . .,		108
8	Conversion and fermentation 		109
9	Distillation 		Ill
10	Purification	,		112
11	Rectification		113
12	Dehydration		115
13	By-product processing 		116
14	Wastewater treatment 		117
A-l	Flow diagram for plant I		152
A-2	Flow diagram for plant II		15 7
A-3	Flow diagram for plant III		163
vii

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TABLES
Number	Page
1	Analytical Parameters and Methods for Alcohol
Plant Process and Effluent Streams 		5
2	Analytical Results/Solids 		9
3	Pesticide Level in Feedstock Grain 		9
4	Analytical Results for Liquid Streams . . . . ....	JL0
5	Analytical Results for Priority Pollutants, Metals,
Total Cyanide, and Total Phenol		15
6	Priority Pollutant Analysis: Volatiles ( g/1) ...	16
7	Priority Pollutant Analysis: Pesticides ( g/1) ...	18
8	Priority Pollutant Analysis: Acid Compounds ( g/1) .	19
9	Priority Pollutant Analysis: Base/Neutral Compounds
( g/1)		20
10	Total Hydrocarbon and Benzene Analysis and Sampling
Data		22
11	Analytical Results and Sampling Data for Ammonia,
Sulfur Dioxide, and Nitrogen Oxide 		23
12	Particulate Matter Analysis and Dryer Cyclone
Effluent Sampling Data 		24
13	Mass and Energy Balances for Conceptual Design ...	36
14	Inputs and Outputs for Steam and Power Generation . .	39
15	Mass Balance for Wastewater Treatment System ....	42
16	Inputs and Outputs of an Alcohol Facility		43
17	Energy and Utility Requirements 		44
1	8	Total. Utility—Requirements . .	- 46
viii

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TABLES (Continued)
Number	Page
19	Air Emissions for an Alcohol Facility		49
20	Summary of Influent Wastewater Characteristics ...	51
21	Solid Wastes Generated by an Alcohol Facility ....	53
22	Alcohol Plant Waste Streams 		55
23	EPA Air Regulations on Standards of Performance for
New Stationary Sources 	 58
24	Summary of State Air Regulations for Fuel Burning
Equipment	 60
25	Summary of Air Regulations for Grain Handling and
Drying	 61
26	State Air Regulations for Incinerators and Volatile
Organic Material 	 62
27	Federal Effluent Quality Standards for Secondary
Treatment	 64
28	Summary of State Water Regulations Potentially
Governing the Alcohol Industry 	 65
29	Boiler Emissions and Environmental Control
Requirements 	 70
30	Particulate Matter Control Options 	 72
31	Fugitive Dust Control Methods 	 75
32	Operating Parameters of Wastewater Treatment
Systems	 78
33	Emission and Effluent Sources 	 85
34	Liquid Sample Preservation and Preparation
Techniques	 90
35	Analytical Techniques for an Environmental
Characterization 	 92
ix

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TABLES (Continued)
Number	Page
36	Alcohol Plant Effluent Sources and Emissions ....	100
37	Sampling/Analytical Matrix - Solids 		101
38	Sampling/Analytical Matrix - Gases 		102
39	Sampling/Analytical Matrix - Liquids 		104
40	Preservation and Preparation Requirements for
Liquid Stream Parameters 		131
A-l Mass Balances Plant I		153
A-2 Mass Balances Plant II		158
A-3 Mass Balances for Plant III		164
B-l Characterization of the Effluents from an Alcohol
Facility		168
B-2 Summary of National Ambient Air Quality Standards .	170
B-3 Ambient Air Increments		171
B-4 States':Air Regulations for Fuel Burning Equipment .	172
B-5 Particulate Emission Standards for Emission
Sources		175
B-6 State Air Regulations for Fugitive Dust and Ground
Level Particulate Concentrations 		181
B-7 States' Ambient Air Quality Standards 		184
B-8 Analysis of Beer Stillage		185
x

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LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS

AA
atomic absorption
BOD
biochemical oxygen demand
COD
chemical oxygen demand
M3
cubic meters
DDG
distiller's dried grains
DS
dissolved solids
FID
flame ionization detection
GC
gas chromatography
HHV
higher heating value
kj
kiloj oules
kPa
kiloPascals
kw
kilowatts
MS
mass spectroscopy
ND
not detected
OVA
organic vapor analyzer
PM
particulate matter
Ppb
parts per billion
PPm 7-
parts per million
SS
suspended solids
TDS
total dissolved solids
THC
total hydrocarbon
TOC
total organic carbon
TS
total solids
TSS
total suspended solids
VDS
volatile dissolved solids
VSS
volatile suspended solids
micro
xi

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ACKNOWLEDGMENTS
This study was conducted by Radian Corporation, McLean,
Virginia, under the direction of Mr. Gilbert J. Ogle, Program
Manager. The program was carried out under EPA Contract No.
68-03-2667. We wish to thank Mr. Paul Mills, the project offi-
cer; Mr. Thomas Powers, the technical project monitor; and Mr.
Robert Mournighan, current project officer for alcohol fuels re-
search; for their direction and cooperation in the conduct of
this program.
We also wish to thank the management and operating staff of
Midwest Solvents' alcohol facility in Atchison, Kansas for their
assistance and cooperation in preparing this document and in con-
ducting the sampling effort. The efforts of Mr. James Mandia,
U.S. EPA Region VII; Mr. Bruce Newton, IPP/NAFC; Dr. William
Telliard, Effluent Guidelines Division, U.S. EPA; Ms. Yvonne
Garbe, Office of Solid Waste, U.S. EPA; Mr. David Markowordt,
Office of Air Planning and Standards, U.S. EPA; Mr. Mike Malloy,
Aerospace Corporation; and Mr. Bill Kuby, Acurex Corporation in
the review of this document are also appreciated.
xii

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SECTION 1
INTRODUCTION
OBJECTIVE
The objectives of this program are to define the require-
ments for environmental sampling and analysis of alcohol-produc-
ing facilities which are developing to support a Gasohol indus-
try, and to apply these requirements to a demonstrated sampling
and analysis effort at a selected alcohol plant.
Background
Ethanol has been used as a fuel mixed with gasoline or alone
as early as the 1930's. Prior to World War II, over 4 million
cars ran on alcohol fuels. The market for alcohol fuels, how-
ever, diminished as gasoline became inexpensive and plentiful. A
systematic investigation of large-scale use of alcohol as a gaso-
line substitute began only with the advent of the energy crunch
in 1 973.
Today the term Gasohol (1) has been coined to describe a
blend of 90 percent unleaded gasoline and 10 percent agricultur-
ally derived ethanol, although ethanol can be used in concentra-
tions up to 20 percent in gasoline without carburetor modifica-
tion. Alcohol is an attractive alternative liquid fuel since it
can be synthesized from renewable biomass sources. As a near-
term gasoline substitute, ethanol can help alleviate the oil
import problem and reduce the balance of trade deficit while pro-
viding a market for farm surpluses or wood and wood residues.
There are many political and economic factors which favor the de-
velopment of a gasohol industry; however, there are also some un-
certainties about the industry which should be investigated. One
of these is the environmental impact of large-scale alcohol-pro-
ducing facilities.
Radian Corporation has conducted a program to define re-
quirements for environmental sampling and analysis of alcohol-
producing facilities which are developing to support a Gasohol
(1) "Gasohol" is a registered trademark of the Nebraska
Agricultural Products Industrial Utilization Committee.
1

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industry, and has applied these requirements to the environmental!
characterization of an alcohol plant. This program was carried!
out under Work Directive S1003 of EPA Contract No. 68-03-2667.
Four interim reports were previously submitted to EPA under this
proj ect.
Approach
To address the first objective, the determination of sam-
pling and analytical requirements for facilities capable of
providing alcohol for Gasohol, the following tasks were
conducted:
•
Task
1 -
Data collection;
•
Task
2 -
Process evaluation;
•
Task
3 -
Review of environmental regulations; and
•
Task
4 -
Assessment of control technology and
requirements.
In the first task, state-of-the-art technology was summa-
rized to identify commercial or pilot plant facilities typical of
those which would support a Gasohol industry. Information on
ethanol and methanol processes utilizing a variety of biomass
materials was collected from technical publications and journals
as well as from contacts with project officers of government
agencies and industrial personnel. A bibliography (page 134) was
assembled containing the sources of information for this task and
was submitted as the first interim report for this program.
To address the second task, the information gathered on al-
cohol technology was assessed to identify several existing alco-
hol beverage plants which employ processing steps similar to
those which might be utilized in future alcohol fuel plants.
Flow diagrams, processing steps, mass balances, and emissions
sources were identified for these plants. These data were pre-
sented in a second interim report and are included in Appendix A.
A detailed mass and energy balance for an alcohol fuel plant con-
sidered to be typical of future alcohol facilities supporting a
Gasohol industry, also presented in the interim report, has been
updated and included in Section 3.
Task 3 consisted of a review of federal and state environ-
mental regulations which might be applicable to fermentation
ethanol facilities. This information is presented in Section 4;
supporting data is provided in Appendix B.
In Task 4, a comparison of the environmental regulations
identified m Task 3 with alcohol stream compositions was made to
2

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define the environmental control requirements necessary for com^
piiance. A discussion of this analysis and designation of the!
probable control technologies to be implemented are presented in
Section 5. The information in Sections 4 and 5 comprised the
third interim report for this project.
To conduct the sampling and analysis of an alcohol plant,
the second objective of this program", a site-specific sampling
plan, was formulated based on the sampling and analytical
requirements determined in the previous tasks. These sampling
requirements and test plan constituted the fourth interim report
of this program and are presented in Sections 6 and 7,
respectively.
A brief discussion of the sampling trip (which highlights
any deviations made in the test plan during sampling and analy-
sis) is included in Section 8. The results and conclusions from
the sample analyses are presented in Section 2.
3

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SECTION 2
CONCLUSIONS AND ANALYTICAL RESULTS OF AN ALCOHOL PLANT
ENVIRONMENTAL CHARACTERIZATION
CONCLUSIONS AND RECOMMENDATIONS
The sampling and analytical requirements for the environmen-
tal characterization of an ethanol-producing facility include:
•	A quantification of the pollutants present in effluent
streams such as pesticides, ammonia, benzene, and metals
in the solid waste streams and by-products; solids, or-
ganics, metals, pH, pesticides and benzene m the liquid
effluents; and criteria pollutants, hydrocarbons, and
benzene in the air emissions.
•	A determination of the effectiveness of environmental
control modules such as condensers on distillation col-
umns and vacuum lines; cyclones, scrubbers, or other
mechanical collectors on stacks or dryer exhausts; and
biological treatment on distillery wastewaters.
•	A characterization of selected internal process streams
to determine the fate of pesticides or benzene losses in
an alcohol plant.
Table 1 presents a summary of the analytical parameters and
methods of analyses necessary to conduct an environmental charac-
terization of an alcohol plant.
As a result of the research conducted in this program, it
was determined that:
•	Alcohol facilities have the potential to cause environ-
mental problems from the discharge of liquid effluents or
air emissions if these streams are not properly treated
or controlled.
•	Untreated distillery wastewaters are acidic and high in
biochemical oxygen demand (BOD), chemical oxygen demand
(COD), and suspended solids (SS).
o Uncontrolled exhausts from by-product distiller's dried
grain (DDG) dryers are high in particulate loading.
4

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TABLE 1. ANALYTICAL PARAMETERS AND METHODS FOR ALCOHOL
PLANT PROCESS AND EFFLUENT STREAMS
Analytical
Parameters
Gases
NO
SO*
CO
particulates
hydrocarbons
benzene
Liquids
solids
organlcs
metals
pH
benzene
pesticides
sulfates
Solids
pesticides
3nnoQici
benzene
metals
Stream
boiler flue gases, dryer off gases
boiler flue gases, dryer off gases
boiler flue gases, dryer off gases
boiler flue gases, dryer off gases
mechanical collectors
boiler flue gases, dryer off gases
fermentation vents, all condenser
vents
dehydration column and striooing
column condenser vents
makeup water, barometer condensate,
cooling tower and ooiler blowdown,
fermenter wash water, wastewater,
treatment influent and effluent
all effluent streams of concern
except boiler blowdown
makeup water, cooling tower and
boiler blowdown, wastewater
treatment influent and effluent
all effluent streams
makeup water, dehydration column
and strlpomg column bottoms,
wastewater treatment influent
and effluent streams
fermenter wash water, flash cooler
condensate, cooker feed, fermenter
outlet, wastewater Influent and
effluent
makeup water cooling tower blowdown,
wastewater treatment influent and
effluent
biological sludge, by-product grains,
feedstock grains
biological sludge, by-product grains,
feedstock grains
Analytical Method
EPA Method 7
EPA Method 6
Orsat analyzer
EPA Method 5
GC w/FID
CC w/FID
EPA 160.1, 160.2,
160.3, 160.4
30D (EPA 405.1)
COD (EPA 410.1)
TOC (EPA 415.1)
AA
pH meterCEPA 150.1)
GC/MS
GC/MS
Gravimetric
GC/MS
EPA 350.2
biological sludge, by-product grains, GC
feedstock grains
biological sludge, by-oroduce grains, AA
feedstock grains
5

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•	NO SC>2 and particulate emissions from fuel oil or coali
combustion for steam generation can be a major environ-
mental problem at an alcohol plant.
•	Solid waste streams, which can be eliminated through re-
cycle and inclusion in the by-products, pose no serious
environmental problems as they are innocuous.
The conclusions listed below are based on the analytical re-
sults (see Section 2 - Results) obtained from the environmental
characterization of an alcohol plant:
Solid Wastes and By-Products
•	The analysis of benzene, pesticides, and ammonia in the
DDG, animal feed, and biosludge streams revealed that no
major environmental problems would be associated with the
discharge or utilization of solid wastes from this alco-
hol plant due to the presence of these compounds.
•	Pesticides identified on feedstock grains were apparently
destroyed during feedstock preparation (i.e., cooking) as
no traces of pesticides were found in the solid wastes or
wastewater effluent streams.
Wastewaters
•	Dissolved solids (DS), the major contributor to total
solids (TS) came from the makeup city water and well wa-
ter, not the fermentation process.
•	Barometric condensate, evaporator condensate, and fermen-
ter wash water were the only significant sources of sus-
pended solids (SS) at the alcohol plant.
•	Benzene does not appear to be a major wastewater problem
for this facility, which employs a benzene dehydration
unit, as it was detected at levels less than 60 ppb in
the wastewater.
•	All wastewater streams from fermentation and distillation
were acidic; they could be an environmental problem if
not neutralized prior to discharge.
•	Extended aeration and clarification reduced high concen-
trations of suspended solids (SS), BOD, COD, total organ-
ic carbon (TOC), and ammonia in the wastewater from this
distiller to acceptable discharge levels.
6

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•	The plant records for this alcohol plant show that excur-
sions in the biological treatment system may occur due to
occasional spills or mechanical problems. Additional
aeration facilities or equilization basins can be employ-
ed to avoid the discharge of poorly treated wastewaters
due to upsets in the current system.
•	Most of the 14 priority pollutants detected at very low
levels (less than 40 ppb) in the wastewaters from this
facility were found to be contaminants from equipment or
the on-site laboratory and not products or by-products of
alcohol production.
•	Total solids (TS) concentration in the bottoms from the
solvent extractor, rectifier, fusel oil column, stripping
column, and dehydration column were very low due to up-
stream removal in the beer still.
Air Emissions
•	Condensers, the only pollution abatement devices for hy-
drocarbons on the vent lines, provided adequate control
for hydrocarbon emissions.
•	Sulfur dioxide and nitrogen oxide emission levels were
low as expected for a facility using natural gas. Com-
bustion of fuel oil or coal could present greater envi-
ronmental problems.
•	The analysis for particulate emissions from the cyclones
on the dryers showed this facility to be in compliance.
However, particulate emissions have a high potential to
be an environmental problem for alcohol plants which dry
their by-product grains or use coal or No. 6 fuel oil for
steam generation.
It must be emphasized that the above conclusions are based
on a single environmental characterization. Additional sampling
and analysis should be conducted at other plant sites to confirm
these initial conclusions.
Rec ommend a t io ns--
Recommendations for further research to ensure that alcohol
plants supporting the Gasohol industry pose no major environmen-
tal problems include:
(1) Gas chromatography/mass spectroscopy (GC/MS) analysis
of pesticide levels in the flash cooler condensate and
the feed stream to the fermenter-to confirm the fate of
pesticides in alcohol synthesis;
7

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(2)	Environmental characterization of other distilleries,
which utilize different feedstocks, processing equip-
ment, fuel sources, and wastewater treatment methods;
(3)	Evaluation of other pollution control technologies to
control emissions and effluents;
(4)	"Performance of" area- monitoring for* "hydrocarbons to de-
termine worker safety information; and
(5)	Analysis for priority pollutant metals should be con-
ducted for the by-product stream to determine whether
these species could build up in concentration when
landfarmed or landspread.
Results--
The analytical results of the sampling effort are presented
below for each of the solid, liquid, and gas streams sampled.
Solids--Table 2 reveals the concentration of benzene, pesti-
cides'] and ammonia (measured as nitrogen content) in the animal
feed, distiller's dried grains (DDG), and biological sludge from
wastewater treatment. The benzene level of the streams was quite
low. No pesticides were detected in any of these streams. The
detection limit for biological sludge (5 percent solids) was low-
er than that for DDG (95 percent solids) since the GC analysis
was conducted using a liquid sample. The nitrogen content of
these streams was also low.
As expected, a variety of pesticides was found in the feed-
stock grain. Gas chromatography indicates the presence of nine
commonly used pesticides in concentrations of 0.003 ppm to 16.2
ppm as shown in Table 3. The gas chromatography analytical tech-
nique applied in this screening effort involved matching elution
of the peaks from the gas chromatography column with standard
values established for these compounds. The precision and accur-
acy of this analytical method is limited due to interferences be-
tween pesticides and other compounds in the sample. However,
this method is sufficient to indicate the presence of pesticides.
The concentration of pesticides can be confirmed in future work
by using gas chromatography analysis in conjunction with mass
spectroscopy as in the priority pollutant analysis.
Liquids--Table 4 presents the analytical results for all
liquiH stream parameters. Each pollutant's parameters will be
discussed separately in the following paragraphs.
Total Solids (TS)--The concentration of TS varied from 13 to
2,735 ppm. The lowest values were for _ the flash cooler con-
densate and evaporator condensate while wastewater treatment
8

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TABLE 2. ANALYTICAL RESULTS/SOLIDS
Analytical
Parameters
Benzene (ppb)
Pesticides
Ammonia (ppm N)
Streams
Animal	Biological
Feed
DDG
Sludge
2.9
15.2
16.2
ND^2)
ND^
ND^
135
135
50
(1)	Average of two determinations
(2)	Detection limit was 10 ppb
(3)	Detection limit was 40 ppb
(4)	Detection limit was 1 ppb
TABLE 3. PESTICIDE LEVEL IN FEEDSTOCK GRAIN
Pesticide Measured	Concentration (ppm)
p, p1-DDT	16.2
Endrin	1.0
DDD and/or 8-Endosulfan	0.1
Dieldrin and/or pf p1-DDE	0.35
a-Endosulfan	0.06
Heptachlor and/or 8-BHC	0.04
Aldrin and/or A-BHC	0.008
Heptachlor Epoxide	0.007
ct-BHC	0.003

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TABLE 4. ANALYTICAL RESULTS FOR LIQUID STREAMS
Analytical	City Cooker
Parameter (ppro)	Hater Feed
Sample Date	8/16 8/16
Total Solids	547
Total Dissolved	547
Solids
Volatile Dissolved 120
Solids
Total Suspended	<1
Solids
Volatile Suspended	<1
Solids
BOD	<1
TOC	2.9
pll (average)	7.46
Benzene (ppb)	10.8
Ammonia (as N)	<1
Pesticides	(2)
Sulfate	190
Copper	<0.1
Iron	0.2
Iodine	<2
Flash
Cooler
Condensate
8/18
13
8
4.5
1880
Fermenter
Outlet
8/17
3.36
ND
Solvent
Extractor
Bottoms
8/18
161
161
<1
1570
533
4.41
ND
Rectifier
Bottoms
8/18
113
113
<1
1440
563
4.67
ND
Fuse]
Oil
Column
Bottoms
8/18
221
218
Dehydration Stripping
Column Column
Bottoms Bottoms
97
36
7.09
8/18
(1)
<1
59.4
8/18
<1
<1
16
11
4.11
5.7
Barometric
Condensate
8/16
2330
300
3204
1790
2.61
(3)
(X)	Sample nol available for analysis*
(2)	Endrln 4.7 ppb; a-Endosulfan 93.8 ppb; Aldrin and/or fi-BlIC 37 ppb.
(3)	DDD and/or B-Endosulfan 9.3 ppb.
ND	Hot Detected (<1 ppb).
(continued)

-------
TABLE 4.(continued)
Analytical
Parameter (ppm)
Evaporator
Condensate
Cooling Tower
Blowdown

Fermenter
Wash
Hater
Well
Water
Wastewater
Treatment
Influent
Wastewater
Treatment
Effluent
Bollei
Blowdoi
Sample Date
8/16
8/17
8/16
8/17

8/18
8/16
8/17
8/16
8/16
8/17

Total Solids
136
74
1450
1350

841
617
640
1200
326
313
2735
Total Dissolved
Solids
68
64
1260
1160

648
599
619
671
309
304
2730
Volatile Dissolved
Solids
68
6 4
364
356


177
86
301
139
130

Total Suspended
Solids
68
10
191
192

193
18
21
530
17
9
5
Volatile Suspended
Solids
67
10
183
190

173
4
5
525
11
9

BOD
3160
(3)
831
(3)

323
2
(3)
93
3
(3)

COD


1090
(3)




2600
20
(3)

TOC
1230
(3)
340
(3)

126
3.5
(3)
828
7
(3)

pH (average)
2.91
2.73
5.30
5.
10
6.13(1)
7.18
7.03
4.32
7.16
6.84
11,
Benzene (ppb)


2.7
3.
0

3.7
3.2
5.0
6.6
27.9

Ammonia (as N)





<1
<1
(3)
42
<1
(3)

Pesticides

ND
ND
ND

ND


ND
ND
ND

Sulfate


520
450


47
55
47
49
52

Copper


0.024
0.
64

<0.05
<0.05
0.95
0.68
<0.05
0,
Iron


8.5
10


8.1
8.0
19
0.35
0.27
0.
Iodine


<2
<2

22
<2
<2
<2
<2
<2

(1)	One determination only.
(2)	Results for 8/17 suspect due to disruption of normal operation.
(3)	Analysis conducted after sample preservation expiration.
ND	Not Detected (<1 ppb).

-------
influent, cooling tower blowdown, and barometric condensate val-
ues were relatively high. Since the beer still removes most of
the solids from the alcohol/water streams, the solids concentra-
tion in all subsequent columns such as the solvent extractor,
rectifier, and fusel oil column was also low. Solids in the
wastewater treatment effluent were also much lower than in waste-
water treatment influent due to biological action.
Total Dissolved Solids (TPS)--The range for TDS was less
than 1 ppm (stripping column bottoms) to 2,730 ppm (boiler blow-
down) . High TDS levels in the boiler blowdown and cooling tower
blowdown are due to the build-up of impurities and water treat-
ment chemicals caused by the evaporation of water. Total dis-
solved solids were the major contributor to total solids m all
of the streams analyzed.
Volatile Dissolved Solids (VPS)--The concentration of VDS
variei from 64 ppm to 364 ppm. Al expected, VPS constitute all
of the dissolved solids for the evaporacor condensate stream and
a large por.tion of the -dissolved solids for the wastewater treat-
ment influent. The dissolved solids for remaining streams were
less than one-third VPS.
Total Suspended Solids (TSS)--Wastewater treatment influent,
cooling tower blowdown, fermenter wastewater, and barometric con-
densate streams were relatively high in suspended solids. TSS
concentration for city water, flash cooling condensate boiler
blowdown, and the bottoms from the solvent extractor, rectifier,
dehydration column, fusel oil column, and stripping column were
near or below the detection limit (1 ppm). Low levels of sus-
pended solids were also found in the well water, wastewater
treatment effluent, and evaporator condensate streams.
Volatile Suspended Solids (VSS)--Most of the suspended sol-
ids found were VSS. In every stream analyzed, except the well
water, VSS comprised 75 to 100 percent of the total suspended
solids, which means that most of the suspended material was or-
ganic in nature.
Biochemical Oxygen Pemand (BOP)—Levels of BOP range from 4
ppm (city water) to 3,204 ppm (barometric condensate) . General-
ly, streams which were found to be high in solids were also high
in BOP. These include barometric and evaporator condensate,
cooling tower blowdown, fermenter wastewater, and wastewater
treatment influent. Exceptions were the flash cooler condensate
and column bottoms from the solvent extractor and rectifier which
have low solids content but high BOP. However, these streams
were also high in dissolved organic compounds (based on TOC
analysis) which also contribute to high BOP values. The BOD for
wastewater treatment effluent and well water was very low.
12

-------
Chemical Oxygen Demand (COD)--Analysis for COD was conducted
for three streams: cooling tower blowdown, wastewater treatment
influent, and wastewater effluent. The values for the first two
streams were very high. The COD for the wastewater effluent was
low, indicating good performance from biological treatment.
Total Organic Carbon (TOC)--Measurements of TOC vary from 3
to 1,790 ppm. The TOC concentration for city water, stripping
column and fusel oil column bottoms, well water, and wastewater
treatment effluent was low. For the remaining eight streams, the
TOC level was one-third to two-thirds the BOD concentration, in-
dicating that organic compounds such as ethanol or fusel oils
account for a large portion of the BOD.
pH--The liquid streams exhibited a pH range of 2.6 to 11.5
with most of the streams being acidic. These include condensate
from the barometric condensers, evaporator, and flash cooler;
column bottoms from the solvent extractor, rectifier, and strip-
ping column; cooling water blowdown; fermenter wastewater; and
wastewater treatment influent stream. Acidity in these streams
is due to the addition of sulfuric acid during fermentation to
retard bacterial growth. Boiler water blowdown was the only
basic stream. The high pH of this stream was due to pH require-
ments for boiler water. Relatively neutral streams include city
water, well water, fusel oil column bottoms, and wastewater
effluent streams.
Benzene--Benzene concentration was reported in the range of
2.7 to 59.4 ppb for the liquid streams. These values are near
the detection limit for benzene and have limited accuracy.
Ammonia--Ammonia concentration, analyzed as ppm nitrogen,
was below the detection limit for all streams except wastewater
treatment influent. Biological treatment reduced this level to
less than 1 ppm in the wastewater effluent.
Pesticides--Gas chromatography indicated the presence of
pesticides in only two streams: feed to the cooker and baromet-
ric condensate. The presence of pesticides in the cooker feed
was expected since traces were found on the feedstock grain. The
existence of these compounds in the condensate stream, however,
was not expected since the pesticides are believed to be destroy-
ed during the cooking process. As mentioned earlier, mass spec-
troscopy can be used with GC analysis to confirm the presence of
pesticides in the streams.
Sulfates--Relatively high concentrations of sulfates were
present in the cooling tower blowdown .and city water makeup
stream. The other streams tested (well water and wastewater
treatment influent and effluent streams) contained moderate
amounts of sulfates. The source of sulfates for the process
13

-------
streams was most likely from the addition of sulfuric acid for pH
control and from the city water makeup stream.
Copper--The concentration for copper was low in all of the
streams, ranging from less than 0.01 ppm in the city water to
0.95 ppm in the wastewater treatment influent stream.
Iron--The concentration of iron varied from 0.2 ppm to 9.0
ppm. High levels of iron were found in the cooling tower blow-
down, well water, and wastewater treatment influent streams.
Iron level in the wastewater treatment effluent, boiler blowdown,
and city water was very low.
Iodine--The concentration of iodine in all streams except
the fermenter wash water was below the detection limit (less than
2 ppm). The analysis indicates the fermenter wash water streams
had an iodine level of 22 ppm, which compares favorably with the
25 ppm concentration that plant personnel reported to be using
for cleaning and disinfection.
Priority Pollutant Analysis-
Tables 5 through 9 present the results of priority pollutant
analysis of the cooling tower blowdown, wastewater treatment in-
fluent, and wastewater effluent stream. The general types of
priority pollutant compounds for which GC/MS analysis was con-
ducted include total cyanides, total phenols, volatiles, pesti-
cides, acid compounds, and base/neutral compounds. Analysis for
metals was conducted using atomic absorption.
Metals, Total Cyanide, Total Phenol—Table 5 presents the
results of priority pollutant analysis of metals, total cyanide,
and total phenol. The results indicate ppb levels of all the
parameters. If present, beryllium, lead, mercury, selenium, sil-
ver, thallium, and total cyanide values were below their detec-
tion limits. The wastewater treatment effluent streams have the
lowest concentration of the parameters detected; all species ex-
cept chromium, copper, and total phenols are highest in the cool-
ing tower blowdown stream.
Volatiles--GC/MS analysis indicated the presence of five
volatile priority pollutants at concentrations of 15 Ug/1 or less
in the streams tested (Table 6). Chloroform and methyl chloride
were detected in the cooling tower blowdown, and benzene and
methylene chloride were detected in the wastewater treatment in-
fluent and effluent streams. The chloroform, methyl chloride,
and methylene chloride were likely to be contaminants from the
laboratory as they are common reagents used in routing analysis.
Toluene, also present in the wastewater treatment influent
stream, was probably associated with the benzene used in dehy-
dration operations.
14

-------
TABLE 5. ANALYTICAL RESULTS FOR PRIORITY POLLUTANTS
METALS, TOTAL CYANIDE, AND TOTAL PHENOL
			Stream		
Analytical Cooling Tower Wastewater Wastewater
Parameter (ppb)	Blowdown	Influent	Effluent
Antimony
18 + 3
10.0 + 5
4.5 +
0.4
Arsenic
7.5 + 1 .5
2.4 + 0.1
0.4 +
0.2
Beryllium
4 + 1
<1
<1

Cadmium
2.5 + 0.4
1 .0 + 0.1
0.3 +
0.1
Chromium
4.4 + 0.1
7.0 + 0.4
1 .2 +
0.1
Copper
24
950
680

Lead
<5
<5
<5

Mercury
<0.2
<0.2
<0.2

Nickel
4 + 2
4 + 2
<0.5

Selenium
<0.3
<0.3
<0.3

Silver
0.72 + 0.02
<0.06
<0.06

Thallium
<2
<2
<2

Zinc
750+10
270+10
<50

Total Cyanide
<20
<20
<20

Total Phenol
56
84
7.5

15

-------
TABLE 6. PRIORITY POLLUTANT ANALYSIS: VOLATILES (yg/1)
	Stream	
Tower Wastewater Wastewater
Blowdown Influent	Effluent
Acrolein
ND
ND
ND
Acrylonitrile
ND
ND
ND
Benzene
ND
1 .6
1 .1
Carbon tetrachloride
ND
ND
ND
Chlorobenzene
ND
ND
ND
1,2-Dichloroethane
ND
ND
ND
1,1,1-Trichloroethane
ND
ND
ND
1,1-Dichloroethane
ND
ND
ND
1 ,1 ,2-Trichloroethane
ND
ND
ND
1 ,1 ,2,2-Tetrachloroethane
ND
ND
ND
Chloroethane
ND
ND
ND
bis (Chloromethyl) ether
ND
ND
ND
2-Chloroethylvinyl ether
ND
ND
ND
Chloroform
5.7
ND
ND
1,1-Dichloroethylene
ND
ND
ND
1,2-trans-Dichloroethylene
ND
ND
ND
1,2-Dichloropropane
ND
ND
ND
1,3-Dichloropropylene
ND
ND
ND
Ethylbenzene
ND
ND
ND
Methylene chloride
ND
15.
6.1
Methyl chloride
3.3
ND
ND
Methyl bromide
ND
ND
ND
Bromoform
ND
ND
ND
Dichlorobromomethane
ND
ND
ND
Trichlorofluoromethane
ND
ND
ND
Dichlorodifluoromethane
ND
ND
ND
Chlorodibromomethane
ND
ND
ND
Tetrachloroethylene
ND
ND
ND
Toluene
ND
1 .6
ND
Trichloroethylene
ND
ND
ND
Vinyl chloride
ND
ND
ND
ND = Not Detected (<1 ug/1)
16

-------
Pesticides--No traces of the 25 commonly used pesticides
were detected In the cooling tower blowdown or wastewater treat-
ment influent and effluent streams as shown in Table 7.
Acid Compounds--Table 8 reveals that four different acidic
priority pollutants were detected in the streams sampled at con-
centrations of 36 ug/1 or lower. The cooling tower blowdown
stream contained 2,4-dimethylphenol, pentachlorophenol, and phe-
nol, while the wastewater treatment influent contained 2-nitro-
phenol and phenol. Sodium pentachlorophenolate is commonly used
to help reduce bacterial growth during fermentation; in the acid-
ic environment of the fermenter, it may degrade to pentachloro-
phenol. Phenol is a by-product in the fermentation process and
is typically found in small amounts along with the fusel oils and
aldehydes. The source of 2,4-dimethylphenol and 2-nitrophenol is
unknown. No acid compounds were detected in the wastewater
effluent stream.
Base/Neutral Compounds — Bis (2-ethylhexyl) phthalate, di-n-
butyl phthalate, and diethyl phthalate were detected in all three
streams at concentrations of 30 yg/1 as shown in Table 9. The
presence of phthalates was likely due to contamination from tub-
ing or other plastic materials which use these compounds as plas-
ticizers. Anthracene and phenanthrene were detected at the 1.5
yg/l level in the wastewater influent stream; the source of these
compounds is unknown.
Gases-
Sampling data and analytical results for air effluent
streams from the alcohol plant are presented in Tables 10 through
12.
Total Hydrocarbons and Benzene—Table 10 presents the re-
sults ol total hydrocarbon and benzene analysis for the air ef-
fluent streams measured as ppm methane. The stream with the
highest concentration of hydrocarbons was the condenser vent on
the stripping column. Benzene accounts for about 9 5 percent of
the hydrocarbons in this stream, which is not remarkable since
the vent lines from the separator and benzene storage tank are
also connected to this vent. The condenser vent on the dehydra-
tion column also had a high concentration of hydrocarbons, half
of which was benzene. Although these vents had high concentra-
tions of hydrocarbons, the total emissions from these sources
were small due to the low gas flow rates from the vents.
The streams with the lowest concentrations of hydrocarbons
were the vent on the dryer cyclone and the fermenter vent. The
flow rates of these streams were relatively large, however, and
the mass emission from these sources was of the same magnitude as
the mass emissions from the stripping column and the dehydration
17

-------
TABLE 7. PRIORITY POLLUTANT ANALYSIS: PESTICIDES (yg/1)
Stream

Tower
Blowdown
Wastewater
Influent
Wastewater
Effluent
Aldrin
ND
ND
ND
Dieldrin
ND
ND
ND
Chlordane
ND
ND
ND
4,4'-DDT
ND
ND
ND
4,4'-DDE
ND
ND
ND
4,4'-DDD
ND
ND
ND
a-Endosulfan
ND
ND
ND
g-Endosulfan
ND
ND
ND
Endosulfan sulfate
ND
ND
ND
Endrin
ND
ND
ND
Endrin aldehyde
ND
ND
ND
Heptachlor
ND
ND
ND
Heaptachlorepoxide
ND
ND
ND
a-BHC
ND
ND
ND
8-BHC
ND
ND
ND
y-BHC
ND
ND
ND
a-BHC
ND
ND
ND
PCB-1242
ND
ND
ND '
PCB-1254
ND
ND
ND
PCB-1221
ND
ND
ND
PCB-1232
ND
ND
ND
PCB-1248
ND
ND
ND
PCB-1260
ND
ND
ND
PCB-1016
ND
ND
ND
Toxaphene
ND
ND
ND
ND = Not Detected (<1 yg/1)
18

-------
TABLE 8. PRIORITY POLLUTANT ANALYSIS: ACID COMPOUNDS (yg/1)
Stream
Tower Wastewater Wastewater
Blowdown Influent Effluent
2,4,6-Trichlorophenol
ND
ND
ND
p-Chloro-m-cresol
ND
ND
ND
2-Chlorophenol
ND
ND
ND
2,4-Dichlorophenol
ND
ND
ND
2,4-Dimethylphenol
36.0
ND
ND
2-Nitrophenol
ND
10.0
ND
4-Nitrophenol
ND
ND
ND
2,4-Dinitrophenol
ND
ND
ND
4,5-Dinitro-o-cresol
ND
ND
ND
Pentachlorophenol
4.2
ND
ND
Phenol
4.5
7.0
ND
ND = Not Detected (<1 yg/1)
19

-------
TABLE 9. PRIORITY POLLUTANT ANALYSIS: BASE/NEUTRAL
COMPOUNDS (yg/1)
Stream

Tower
Blowdown
Wastewater
Influent
Wastewater
Effluent
Acenaphthene
ND
ND
ND
Benzidine
ND
ND
ND
1,2,4-Trichlorobenzene
ND
ND
ND
Hexachlorobenzene
ND
ND
ND
Hexachlorobenzene
ND
ND
ND
bis(2-Chloroethyl) ether
ND
ND
ND
2-Chloronaphthalene
ND
ND
ND
1,2-Dichlorobenzene
ND
ND
ND
1,3-Dichlorobenzene
ND
ND
ND
1,4-Dichlorobenzene
ND
ND
ND
3,3'-Dichlorobenzidine
ND
ND
ND
2,4-Dinitrotoluene
ND
ND
ND
2,6-Dinitrotoluene
ND
ND
ND
1,2-Diphenylhydrazine
(as azobenzene)
ND
ND
ND
Fluoranthene
ND
ND
ND
4-Chlorophenyl phenyl
ether
ND
ND
ND
4-Bromophenyl phenyl
ether
ND
ND
ND
bis(2-Chloroisopropyl)
ether
ND
ND
ND
bis(2-Chloroethoxy)
methane



Hexachlorobutadiene
ND
ND
ND
Hexachlorocyclopentadiene
ND
ND
ND
Isophorone
ND
ND
ND
fD = Not Detected (<1 yg/1)



(continued)
20

-------
TABLE 9. (continued)
Stream

Tower
Blowdown
Wastewater
Influent
Wastewater
Effluent
Naphthalene
ND
ND
ND
Nitrobenzene
ND
ND
ND'
N-Nitrosodimethylamine
ND
ND
ND
N-Nitrosodiphenylamine
ND
ND
ND1'
N-Nitrosodi-n-propylamine
ND
ND
ND
bis(2-Ethylhexyl)
phthalate
30
22
10'
Butyl benzyl phthalate
ND
ND
ND
Di-n-butyl phthalate
2.5
5.5
1.6
Di-n-octyl phthalate
ND
ND
ND
Diethyl phthalate
2.8
7.5
1.5
Dimethyl phthalate
ND
ND
ND
Benzo(a)anthracene
ND
ND
ND
Benzo(a)pyrene
ND
ND
ND
3,4-Benzofluoranthene
ND
ND
ND
Benzo(k)fluoranthene
ND
ND
ND
Chrysene
ND
ND
ND
Acenaphthylene
ND
ND
ND
Anthracene
ND
1.5
ND
Benzo(ghi)perylene
ND
ND
ND
Fluorene
ND
ND
ND
Phenanthrene
ND
1.5
ND
Dibenzo(a,h)anthracene
ND
ND
ND
Indeno(1,2,3-c,d)pyrene
ND
ND
ND
Pyrene
ND
ND
ND
2,3,7,8-Tetrachloro-
dibenzo-p-dioxin
ND
ND
ND
ND = Not Detected (<1 yg/1)
21

-------
TABLE 10. TOTAL HYDROCARBON AND BENZENE ANALYSIS AND SAMPLING DATA
Gas	Pipe Avg. Gas Avg. Gas	Avg. Con-
Sample	Sample	Temp. or Duct Velocity Flow Bate	tratlon Emissions
Stream/Parameter	Date	Time	(°C) (ID-cm) (M/s) (Dry H /hr)	(ppm CH^) (kg CH^/hr)
Ferraenter Vent
TIIC	8/18	1603-1708	2,960*1*	95.7	0.19
Beer Still
Condenser Vent
TIIC	8/18	1734-1836	65.6	10.8	12,800	74	219	.011
Solvent Extractor
Condenser Vent
THC	8/18	1214-1325	48.9	10.2	1,460	9.4	1,710	.011
Rectifier Condenser
Vent
IHC	8/18 1845-1936 37.8 10.8	<90	—	1,530
Fusel Oil Column
[\J	Condenser Vent
TIIC	8/18 1103-1207 79.4 10.8	1,140	4.6	973	.003
Dehydration Column
Condenser Vent
TIIC	8/17	1412-1512	37.8	5.1	1,335	2.5	29,900	0.050
Benzene	1548-1555	17,000	0.027* '
Stripping Column
Condenser Vent
TIIC	8/17	1200-1232	37.8	5.1	1,370	2.5	55,400	.095
THC	1320-1348	55,200	-095/«
Benzene	1817-1825	52,900	0.090* '
Cyclone Vent
on Dryer
THC	8/17	0912-1003	98.9 158.8	55,600 63,960	7.7	0.33
(1)	Total gas flow rate from all fermenters based on hourly plant production.
(2)	lliis Is equivalent to 0.31 kg/hr benzene.
(3)	This is equivalent to 0.98 kg/hr benzene.

-------
TABLE 11. ANALYTICAL RESULTS AND SAMPLING DATA FOR
AMMONIA, SULFUR DIOXIDE, AND NITROGEN OXIDE
Stream/
Analytical Parameter
Sample
Time L Date
Gas Vol.
Samnled
(M )
Total
UL. of
Speclea
Collected
(i»k)
Gas
Phase Con-
tration
(ppm)
Gas
Flow Rate
(M /hr")
Emission
(kg/hr)
Ferinenter Vent
8/17

<430(1)
<430(1)



mi3 III
N»3 02
1613-1740
1744-1910
0.40
0.42
<1.5
<1.5
2,970
2,970
<0.003
<0.003
Cyclone Effluent (Dryer)
a/io





Nll3 01
13-05-1455
1.0
2,420
3.27
63,960
.15
Ullj 112
S02 111
1911-2038
1114-1244
0.82
0.86
700
<650(1*
1.19
<0.3
63,960
63,960
0.051
.<0.050
S02 It 2
1739-1907
0.76
<650(l*
<0.3
6*3,960
<0.050
NO 01
X i
1020
0.0013
67.5
26.1
63,960
X.4<2>
NO #2
X
1022
0.0014
29.4
10.7
63,960
0.58*2*
NO US
X
1433
0.0013
21.9
8.3
63,960
O.50*2*
NO 0/i
1558
0.0012
79.1
32.7
63,960
1.7<2>
(1)	Detection Limit
(2)	I.b/hr of NO^

-------
TABLE 12. PARTICULATE MATTER ANALYSIS AND DRYER CYCLONE
EFFLUENT SAMPLING DATA
Sampling Time
Gas Volume Metered (M^)
3
Standard Gas Volume (M )
Average Flue Gas Velocity (M/s)
Average Flue Gas Temp. (°C)
Stack Pressure (kPa)
Flue Gas Composition
h2o
CO,
°2"
CO
*2
Flue Gas Molecular Weight
Flue Gas Total Flow (Actual M^)
(M^/aour)
Duct Diameter (M)
Flue Gas Grain Loading (grams/H^)
Filter Weight Gain (grams)
PTobe Wash Weight Grain (grams)
Particulate Flow Rate (kg/hour)
Sample Percent Isokinetic
Particulate
Samole itl
8/16
1114-1455
2.0
1.9
14.0
98.9
102
19.2, .
5.0
6.5
0
69.3
27.14
1,670
63,390
1.6
0.04
0.02589
0.05749
2.8
110.9
Particulate
Sample #2
8/16
1739-2038
1.8
1.7
14.1
88.3
102
20.4
5.1
0.5
0.6
73.4
26.80
1,670
64,240
1.6
0.02
0.01741
0.02198
1.5
108.9
24

-------
column. The flow rate from the condenser vent for the rectifier,
was too low and variable to measure. The hydrocarbon concentra-
tions and emissions for the condenser vents on the beer still,
solvent extractor, and fusel oil column were very low.
Ammonia--Samples were taken from the fermenter vent and the
dryer cyclone effluent stream for ammonia analysis. As Table 11
illustrates, the ammonia concentration in both streams was very
low and total emissions from both streams were less than 0.8
kilograms per hour.
Sulfur Dioxide and Nitrogen Oxide—Table 1 1 also presents
the SO2 and NOx results for the dryer cyclone effluent
stream. The SO2 concentration was below the detection limit.
Nitrogen oxide concentrations were below 35 ppm, which corre-
sponds to an emission of less than 1.8 kilograms per hour NC>2 •
Particulate Matter—Table 12 presents the results of partic-
ulate matter analysis along with sampling data for the effluent
stream for the dryer cyclone (flue gas). Particulate emissions
were calculated to be 1.4 to 2.7 kilograms per hour with partic-
ulate loading measured at 0.02 to 0.04 grams per m3 . Also
presented in this table is the composition of the flue gas.
25

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SECTION 3
ALCOHOL PROCESS EVALUATIONS/CONCEPTUAL DESIGN
This section presents a conceptual design of a fermentation
alcohol plant likely to support a Gasohol industry.^ The major
unit operations of the facility are identified and a schematic
flow diagram is presented to show internal stream routing. This
diagram also forms the framework for mass balances around the
major pieces of equipment. Included in the conceptual design
discussions are a list of assumptions and a summary of the energy
requirements. In light of the rapid political and technological
changes presently occurring in the Gasohol field, however, pre-
diction of even the major processing steps must be considered
tentative.
Stream flow rates are based on actual plant data while prop-
erties were taken from the literature. From this design, esti-
mates were prepared for the sources, levels, and flow rates of
potentially hazardous emissions and effluent streams generated by
a future alcohol plant.
FERMENTATION ETHANOL PRODUCTION
Before discussing the more complicated flow diagram prepared
for the conceptual alcohol plant design, a simplified model con-
taining processing units necessary for any fermentation ethanol
process will be described. Figure 1 depicts a generalized flow
scheme for a fermentation alcohol facility and illustrates the
four essential steps to produce anhydrous ethanol:
•	Feedstock preparation;
•	Fermentation;
•	Distillation; and
•	Dehydration.
1 Flow diagrams and mass balances have also been prepared for
three existing fermentation ethanol plants. This information has
been presented in a previous report and is reiterated in Appendix
A of this document.
26

-------
co2
Product
Alcohol
Byproduct
Drying
Feedstock
Preparation
Fermentation
Distillation
Dehydration
K>
Process
Stream
Process
Power
Coal

1



Boiler

Power


Plant
Cooling
Water
Cooling
Tower
Supporting Facilities
Wastewater
From Plant
Wastewater
Waste
Discharge
Sludge
Figure 1. Flow diagram for an alcohol facility.

-------
The first two steps include biological processes. The feed-
stock preparation step consists of breaking down the starch
(polymer of sugar molecules) of the biomass into individual sugar
molecules. This includes grinding, cooking, and enzyme conver-
sion. In the next step, fermentation, the yeast converts the
sugar to ethanol and carbon dioxide according to the equation be-
low :
c6h12°6 yeast 2C2H5OH + 2C02.
The third step, distillation, removes unreacted feedstock
material sucn as protein, fibers, oils, and a small amount of
sugar; it also concentrates the solution by separation from
water. A portion of the unreacted material can be recycled to
fermentation, but most is dried and sold as a by-product (animal
feed). Dehydration removes nearly all the remaining water; this
step is necessary to produce a fuel product.
Supporting facilities necessary for any plant include the
equipment for the steam and power generation required by the pro-
cess, a cooling tower, and a wastewater treatment system.
Conceptual Design of an Alcohol Fuel Plant
Although the five facilities currently providing ethanol for
Gasohol are converted alcohol beverage plants, in the next 5 to
10 years most of the necessary capacity will be generated by
"grassroots" facilities using, for the most part, conventional
fermentation technology. A conceptual design was developed to
reflect such a facility that might be built in that time period.
After a short discussion of the criteria used in selecting
the flow scheme, a list of assumptions used to develop the mass
and energy balances is presented. Following the mass balance
sheets and the flow diagrams is a summary of the overall mass and
energy inputs and outputs of the plant. This subsection con-
cludes with a discussion of the environmental impact of an alco-
hol facility, including an estimate of the probable emission
factors according to their sources, flow rates, and levels of
pollutants.
Criteria Used for Selection of Processing Steps--
The logical basis for any consideration of a fermentation
alcohol plant is the established distillery industry. As cited
previously, however, distinct differences exist between fuel
grade and a beverage grade alcohol product. These differences
lie primarily in the purity and water content of the alcohol.
Significant alterations of the processing equipment and proce-
dures required for fuel grade ethanol will result from these
operating conditions in the distillation sequence and additional
separation columns which are unnecessary in an alcohol fuel
28

-------
plant. On the other hand, ordinary distillation techniques are
unable to remove the 4 to 5 percent water in aqueous alcohol;
even this small amount of water in ethanol/gasoline mixtures
causes phase separation. To produce anhydrous (water-free) etha-
nol for fuel use, the remaining water must be extracted using a
third component. Other process changes are also possible and are
included in the plant design.
More modern equipment has also been incorporated into the
conceptual design. For example, low moisture (less than 9 per-
cent) distiller's dried grains (DDG) can be efficiently dried by
a pneumatic dryer using air directly heated by combustion flue
gases. The moisture laden effluent air is then scrubbed for re-
duction of particulates and SO2 before being vented to the at-
mosphere. Each processing step or procedure was selected as an
attempt to reflect the probable construction and operation of a
future grassroots fuel alcohol facility.
Assumptions--
The assumptions made in developing a conceptual design were
carefully chosen to reflect current or planned practices in the
alcohol industry. These assumptions may be grouped into material
balance, power and steam production, and emissions-related
assumptions.
Material Balance Assumptions--
(1)	Throughput for the plant is 198 cubic meters per day of
absolute alcohol, or 6,516 kilograms per hour for an
annual production of 436,200 cubic meters per year at
an 80 percent operating rate.
(2)	Corn is the feedstock.
(3)	An anhydrous product (less than 0.3 percent water) will
be produced.
(4)	Fusel oils and aldehydes will remain in the product al-
cohol, nominally at concentrations of 1.25 percent.
(5)	A standard distiller's yeast (Saccharomyces cerevisiae)
is selected for reaction in the batch fermentation pro-
cess .
(6)	Fungal amylase is the saccharifying enzyme used to hy-
drolyze the starch.
29

-------
(7)	By-products are CO2, which can be vented or collected
and'sold, and an animal feed supplement known as di~s^
tiller's dried grains (DDG).
(8)	A cooling tower for recirculation of plant cooling
water is assumed; a temperature rise of 17°C in the
water used for plant cooling equipment is typical.
(9)	In the assessment of alcohol plant emissions, the envi-
ronmental load is a strong function of the energy re-
quired. This is because a large portion of the total
plant effluents are generated from heat and power pro-
duction. In general, many more heat recovery tech-
niques, particularly in the distillation section, could
be implemented to lessen the energy requirements. Be-
cause of the great variety of these heat recovery pro-
cedures, no attempt was made to include more than basic
conservation techniques in this initial design.
(10) In general, heat, losses, unless conjectured to be sig-
nificant, were neglected in making the energy balances.
Power Production--
(1)	Saturated process steam is produced at 1,035 kPa (181°
C) and 297 kPa (121 °C) .
(2)	The cleanup required from a coal-fired boiler would of-
fer great incentive for the use of oil-fired units in
the' near term. The current policy, however, is that
grassroots plants must have coal-firing capability.
Therefore, an Illinois No. 6 coal is used as the main
fuel source for steam and power production. The fol-
lowing is the ultimate analysis (as-received basis) of
the coal:
C
66.3 wt %
H2
°2
N2
Ash
4.5
7.5
1 .3
1 1 .7
S
2.7
H20
5.8
HHV
5,5-80 kj/kg
30

-------
(3)	A spreader stoker coal furnace is used with a boiler-
efficiency of 80 percent (heat losses of 20 percent).
(4)	Total air at 145 percent of theoretical air is used in
firing the coal. Complete combustion is assumed.
(5)	Bottom ash from the spreader stoker boiler is assumed
as 35 percent of the total ash in the coal feed.
(6)	For the fuel service	to the dryer furnace, a No. 2 dis-
tillate fuel oil was	selected of the following composi-
tion:
C	8.2 wt 7o
H	12.5
0	Nil
N	0.02
S	0.3
Ash	Nil
HHV	9,270 kj/kg
(7)	Excess air (60 percent relative humidity and 27°C dry
bulb) of 10 percent is used to fire the fuel oil. Com-
plete combustion is assumed.
(8)	A flue gas temperature of 427°C and heat losses of 20
percent are assumed.
Emissions--
(1)	Emmission factors for the coal-fired boiler and the
oil-fired dryer furnace are adopted from both combus-
tion calculations and the EPA report, "Compilation of
Air Pollutant Emission Factors," AP-42 (third edition).
(2)	On-site wastewater treatment using extended aeration as
the biological treatment process was chosen. Effluent
sludge is to be recycled to the dryer for inclusion
with the DDG.
(3)	Cooling water blowdown is assumed at 10 percent of the
total cooling water requirement.
31

-------
Flow Diagnosis of an Alcohol Facility
A conceptual design of an alcohol facility that might sup-
port a Gasohol industry appears in Figures 2 and 3. Supporting
data is given in Tables 13 and 14.
The process begins by grinding shelled corn in a hammer mill
before dilution with water and recycled stillage from the beer
still bottoms. Steam is injected to raise the temperature, which
aids in solubilizing the mash, thus forming a more suitable sub-
strate for enzymatic hydrolysis. Retention times in the range of
1 to 2 minutes are maintained in the continuous pipeline pressure
cooker. The cooked material is cooled to 63°C by evaporating
some of the water under vacuum.
Fungal amylase is added in the conversion tank as the hydro-
lytic enzyme that breaks down the starches to fermentable sugars.
Use of the amylase is a notable difference from conventional bev-
erage plants; both federal regulations and final product flavor
require distillers to use enzyme directly derived from the malt-
ing of barley.
After the cooked mash is cooled to 27°C, it is introduced
into the batch fermentation vessels. Yeast is added and the tem-
perature controlled at 270°C in the water-jacketed reactors. The
low strength fermented mash (10 percent alcohol) is pumped to the
beer still overhead heat exchanger where the feed is heated to
93°C. The heated stream is introduced into the top of the beer
still. This column separates the solids and much of the water
from the alcohol.
Because the final product is ethanol for fuel, the aldehyde
column and the fusel oil purification column(s) found in beverage
grade alcohol plants may be eliminated. The overheads from the
beer still are fed to the rectifier, where 95 percent alcohol is
produced. Fusel oils (mostly amyl alcohols) are removed from the
lower part of the column and added to the feed to the dehydration
unit. Again, this is permissible in a fuel grade plant because
fusel oil contamination does not affect the combustion of etha-
nol. Water is removed at the rectifier bottoms and sent to
wastewater treatment.
Dehydration of the alcohol is necessary to produce an anhy-
drous product suitable for blending as a motor fuel. Benzene has
been selected as the drying agent, although other solvents have
been investigated (notably ethyl ether). The overheads from the
benzene dehydration column which are cooled in a separator form
two layers. The water/alcohol-rich bottpm layer containing re-
sidual solvent is routed to the benzene recovery column where the
benzene is separated and recycled to the dehydration column. The
benzene/ethanol-rich top layer is recirculated to the benzene de-
32

-------
Pron
Rectifier J —
Overheads
Fueel Oils
Fro®
Rectifier
Dehydra-
tion
Column
45.
Anhydrous
Alcohol
Product
Figure 2.
Flow diagram for conceptual design.

-------
recc-added
Condenser
Corn
llaouwr
Hill
Grinding
Conclnuoue)Flash
Cooker pooler
Holding
freer Well
U>
i
-------
© .
©

Boiler
(?) ,
©


© ©
<»
©
1 ~
Power
Plant
©
Figure 3. Steam and power generation.
35

-------
TABLE 13. MASS AND ENERGY BALANCES FOR CONCEPTUAL DESIGN
Composition
Stream Origin and Destruction	kg/hr	Wt%
1
Corn to hammer mill
21
320

2
Makeup water to cooker (from flash
condensate)
23
450

3
Steam to cooker
12
500

4
Saccharifying enzyme to conversion
tank
2
130

5
Cooling water to direct-cooled
condenser
162
950

6
Condensate from flash cooler to
cooling water system
146
500

7
Cooker mash to conversion tank
59
950

7a
Cooling water to mash cooler
97
580

8
Yeast slurry to fermenter
9
430


yeast
4
350
46

water
5
080
54
8a
Converted mash to fermenter
62
100

9
CO2 from fermentation
6
360

9a
Cooling water to fermenter jacket
75
000

10
Beer from beer well to beer still
65
160


ethanol
6
520
10

water
51
730
79.4

solids
6
930
10.6
11
Steam injected into beer still
3
850

12
Cooling water for overhead condenser
136
360

13
Beer still overheads to rectifier
8
150


ethanol
6
520
80

water
1
550
19

fusel oils

82
1
14
Beer still bottoms to centrifuge
60
860


water
53
930
88.6

solids
6
930
11.4
15
Centrifuge cake to dryer
15
820


water
10
270
65

solids
5
550
35
16
Thin liquids from centrifuge to
evaporator
45
050


water
43
640
96.9

solids
1
410
3.1
(continued)
36

-------
TABLE 13. (continued)
Composition
Stream Origin and Destruction	kg/hr	Wt%
17
Recycle thin stillage to cooker
14,770


water
14,320
96.9

solids
454
3.1
18
Steam to multi-effective evaporator
(@ 30 psig)
7,810

19
Cooling water to evaporator condenser
161,450

20
Evaporator return to cooling water
system
168,950

20a
Water to secondary treatment
20,500

21
Cake from evaporator to dryer
1,850


water
915
49.5

solids
935
50.5
22
No. 2 fuel oil to dryer furnace
1,070

23
Combustion air (10% excess)
16,770

24
Hot flue gas from furnace to dryer
92,820

25
Distillers dried grain
7,120


water
640
9.0

solids
6,480
91.0
26
Dryer off gases to scrubber
103,730


water
10,860
10.5

air
92,860
89.5
27
Makeup water to scrubber
Fluctuates
28
Wastewater to treatment system
12,440

29
Vent gas to stack
10,695


water
14,180
13

air
92,800
87
30
Fusel oils from rectifier to
dehydration column
70

31
Bottoms from rectifier to WW treatment
1,550


(water)

32
Steam to rectifier reboiler (150 psig)
9,080

33
Cooling water from rectifier condenser
280,100

34
190 proof ethanol to dehydration
column
7,140


ethanol
6,860
96

water
780
4
(continued)
37

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35
36
37
38
39
40
41
42
43
44
45
TABLE 13.(continued)

Composition
Origin and Destruction
kg/hr
Wt%
Recycle from benzene recovery to
630

rectifier


ethanol
340
54.4
water
290
45.6
Reflux to dehydration column
4,480

ethanol
600
13.4
water
90
2.1
benzene
3,790
84.5
Overheads from dehydration column
5,710

ethanol
945
18.5
water
380
7.4
benzene
'3,785
74.1
Benzene makeup
Variable

Bypass reflux
520

ethanol
95
18.5
water
40
7.4
benzene
390
74.1
Feed to separator
4,630

ethanol
860
28.5
water
340
7.4
benzene
3,430
74.1
Feed to benzene recovery
670

ethanol
350
52.0
water
290
43.1
benzene
32
4.9
Overheads from benzene recovery
45

ethanol
9
19.2
water
3
7.1
benzene
33
72.7
Cooling water to dehydration condenser
45,450

Steam to dehydration reboiler
1,610

Anhydrous ethanol production
6,520

38

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TABLE 14. INPUTS AND OUTPUTS FOR STEAM AND POWER GENERATION
Flow Rate
Stream Description	(kg/hr) T(°C) H(kj/kg)
1	Coal feed to main boiler	4,770 Ambient inr-5,580
2	Combustion air	62,090 Ambient
(27° and
60% RH)
3	Process steam, saturated
at 150 psia	27,045 181	570
at 30 psia	7,815 121	557
4	Steam to drive power plants 5,000	18	570
5	Flue gas from main boiler	67,550 180
C02	11,590
H20	3,000
S02	258
NO	40
X
0*2 (excess)	4,555
N2	47,820
Unburned hydrocarbons	7
Fly ash	366
6	Bottom ash from main boiler 1,090
7	Power required in main	76 kw
boiler
8	Process power	976 kw
39

-------
hydration column as reflux. Aqueous alcohol from the benzene
recovery unit bottoms is also recycled to the rectifier feed for
water removal.
By-product CO2 recovered from fermentation may be purified
through a scrubbing train and sold; producers may choose to vent
this stream to the atmosphere. Trace amounts of alcohol vapor
may be present in this stream when vented.
Beer still slops are centrifuged for the removal of the
majority of the solids. A portion of the centrate (thin still-
age) is recycled and the remainder evaporated in a multi-effect
evaporation unit for further removal of the solids. The wet cake
(35 percent) from the centrifuge is mixed with the evaporated
solids and augered to a flash drying system; hot flue gases and
air pneumatically convey the granular material through the verti-
cal drying duct, vaporizing most of the surface moisture. A cy-
clone is used for solids separation and the dried material is
collected and sold as distiller's dried grains (DDG). The flue
gas stream, still carrying some entrained solids, is sent to a
wet centrifugal scrubber for solids removal before ventilation to
the stack. The scrubbing liquor is recycled, with a continuous
blowdown piped to the wastewater treatment system.
Two support furnaces are required in this alcohol plant. An
oil-fired furnace provides the hot gases to the dryer, and main
process steam is generated in a coal-fired spreader stoker boil-
er. It should be noted that combustion products from these units
form the bulk of the air emissions.
The wastewater treatment system is shown in Figure 4 with
supporting data contained in Table 15. An extended aeration-
activated sludge system was selected including secondary sedimen-
tation, recycle of some solids, and recirculating the remaining
effluent sludge to the flash drying system for addition to the
animal feed by-product. A more extensive discussion of the
plant's air, water, and solid effluents is found in the Emis-
sions section.
Discussion of Conceptual Design
Based on the alcohol production rate of 190 m3 per day
(57,820 M3 per year at an 80 percent operating rate) of anhy-
drous alcohol, Table 16 presents the overall inputs and outputs
to the alcohol facility. As discussed earlier in the Assumptions
section, energy consumption in the plant was calculated assuming
the aplication of only minimal heat recovery techniques. The re-
sulting energy and utility requirements are presented in Table
17.
40

-------
©
Extended
Aeration
Activated Sludge
'
r
Settling
Basin

©
©
Figure 4. Wastewater treatment facility.
41

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TABLE 15. MASS BALANCE FOR WASTEWATER TREATMENT SYSTEM
Stream Origin and Description	Flow Rate
1	Wastewater from plant	2,400 M"Vday
2	Treated water to river	2,270 M^/day
3	Sludge (50 percent solids)	to 45 kg/hr
1andfarming
42

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TABLE 16. INPUTS AND OUTPUTS OF AN ALCOHOL FACILITY
Material
INPUT
Corn @ 56 lb/bu
Enzyme
Yeast
Benzene
Coal
Oil
OUTPUT
Alcohol (100%)
Carbon Dioxide
Distiller's Dried Grains
Sludge
Input or Output
g/M^ Ethanol
37
3.7
7.6
Enough to Replace
Losses
8.3
1.9
11.2
11.0
12.4
0.79
Total
(kg/hr)
21,330
2,130
4,350
4,770
1,070
6,520
6,360
7,120
45
43

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TABLE 17. ENERGY AND UTILITY REQUIREMENTS
Utility Required
Btu
Steam
(Saturated @
1,035 kPa)
(Saturated 0
207 kPa)
Fuel Oil
(No. 2 distillate)
Electric Power
Cooling tyater
Coal
(Illinois No. 6)
By-Product
Prying
kj/M3
117
13.8 g/M
1.9 g/M
0.9 j/M
19.6 H3/H3
Cooking,
Grinding,
Distillation Fermentation
51
kj/M3 45 kj/M3
25.3	g/M
0
0.08 j/M3
55.9	M3/M3
21.7	g/M
0
0.5 j/H3
40.8	H3/H3
Steam
Generation
Auxiliaries Requirements
0.7 kj/M
0.2 j/M
21 kg/M
8.6 g/M
0.6 j/M
19.1 M3/M3
Total Per H
61,900 kj
13.8 g
1.08 lb
23 J
135.9 M
Tota) Per Hour
134,748,000 kj
32,050 kg
7,800 kg
1,070 kg
1,306 kv
1,116 M3
4,560 kg

-------
The required steam and power are generated by the combustion
of coal. Some designs have attempted to use the stover (corn-
stalks, husks, and cobs) associated with corn production as a
fuel source, thereby improving the net energy balance. This
seems unlikely due to the cost of collection and transportation
as well as solids handling problems at the plant. Removal of
stover from the original field also increases the fertilizer re-
quirement and mandates more stringent land erosion control. For
these reasons and the federal requirement that energy sources m
grassroots facilities be non-fuel oil-fired, a steam and power
plant firing an Illinois No. 6 coal was selected.
A recirculating cooling water system was selected with the
following operating parameters:
•	Permissible temperature rise of 17°C;
•	Ten percent blowdown rate;
•	Maximum temperature of 32°C permissible in water returned
to process; and
•	Pumping requirements of 265 kw/1,000 M^/p.
In addition to coolers and condensers located in the pro-
cess, cooling water is required in the power plant for heat ex-
changers on 0.12 M^/S/kw generated. The power plant turbines
also require 3.83 kilograms steam per kilowatt hour. Finally,
the boilerhouse auxiliary equipment (pumps, fans, etc.) consume
212 kilowatt hours for every 1,000 kilograms of steam generated.
These data and the total requirements are presented in Table 18.
Long-Term Developments Which Might Affect the Design--
Every attempt was made to design a facility that would be
representative of plants supporting a Gasohol industry. Many
other processing steps, routes, or procedures currently or po-
tentially available could be implemented. Areas of research
include:
•	Continuous fermentation under vacuum;
•	Elimination of the rectifying column;
•	Use of various extraction solvents; and
•	Alternate feed stock sources.
Continuous Fermentation—Two routes for continuous fermenta-
tion are currently proposed. One pathway employs a series of
continuous stirred tank reactors and yeast centrifuges for
45

-------
TABLE 18.
Utility	Process Rate
Steam
1,035 kPa	27,050 kg/hr
207 kPa	7,800 kg/hr
4> Electricity	976 kw
cr>
Cooling Water
960 M3/s
TOTAL UTILITY REQUIREMENTS
Utility
Generation
Requirement
3.8 kg/kwh
265 kw/1,000 M3/s
2.2 kwh/1,000 kg
0.12 M3/s
Amount Consumed
in Generation
of Utilities
500 kg/hr
0 kg/hr
253 kw
i 76 kw
160 M3/s
Total Rate
32,050 kg/hr
7,800 kg/hr
1,300 kw
1,100 M3/s

-------
recycling the active yeast to the process. The most significant
problems include difficulty in separation of the yeast by mechan-
ical means from the unconverted mash and low levels of output al-
cohol concentration necessitated by its toxic effects on the
yeas t.
The latter problem is also the major deterrant to a scheme
that uses a packed column; the bed material provides a fixed "s'ub—
strate for attachment of the yeast. Researchers have suggested
development of a high alcohol tolerance organism or a series of
intermediate product draws as methods of circumventing the toxic-
ity problem.
The second pathway is continuous fermentation under vacuum
(4 to 5 kPa) that eliminates the need for costly distillation
steps. Product alcohol is vaporized as it is formed in the fer-
mentation vat. Supportive research at Cornell University (41)
indicates that the energy savings achieved by using the heat from
the exothermic fermentation reaction to distill off the alcohol
is offset by the pumping requirements necessary to maintain the
reduced pressure and bring the CO2 off gas up to atmospheric
pressure. However, capital costs for the vacuum fermentation
scheme are lower than for conventional batch fermentation with
distribution. The development of a thermophilic yeast strain vi-
able at temperatures of 40°C to 50°C would mean lower vacuum re-
quirements and would be one way to circumvent these problems.
Vacuum fermentation technology has been developed in Switzerland
and is soon to be tested here in the United States.
Elimination of the Rectifying Column—Some experimentation
is currently underway in eliminating the rectifying column by in-
creasing the height of the beer still and introducing an interme-
diate reboiler. Relaxation of the product quality requirements
in fuel grade ethanol presents the major impetus for this option.
Use of Various Solvents for Extraction—Benzene is one of
the many solvents suitable for the azeotropic distillation of an
ethanol-water system. Other solvents are also under intensive
investigation - ethyl ether, hexane, or a gasoline cut. The lat-
ter is of particular interest because less solvent recovery is
necessary. The component ratios required in the feed to the de-
hydration column for proper operation are less rigid for a system
using a gasoline cut. Further, the energy consumption is also
lessened. However, safety, cost, and transportation questions
have yet to be answered.
Alternate Feedstock Sources—Other sources of biomass are
continually being researched as raw materials for fermentation
processes. These include agricultural and forestry wastes, high
starch terrestrial or aquatic "energy" crops, and urban and
industrial wastes. The most promising sources of feedstocks for
47

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fermentation ethanol plants in the next decades appear to be for-
est, agricultural, and urban wastes. Because the infrastructure
for collection and transportation of urban wastes already exists,
an economic incentive favoring the use of this source exists.
None of these, however, are likely to supply alcohol plants in
the near future.
ENGINEERING AND DESIGN
At this level of design, little peripheral equipment was in-
cluded. These units will only slightly increase the total energy
consumption. In addition, plant layout and location, which would
also impact the engineering design, are beyond the scope of this
report.
Emissions
Based on the conceptual design, the major streams of envi-
ronmental concern were identified and quantified according to
air, water, and solid waste impacts.
Air--
Values of air emissions for the alcohol facility appear in
Table 19. The principal air pollutants from this plant are gen-
erated from the main boiler coal combustion. As indicated ear-
lier, the selection of a coal-fired boiler was influenced by fed-
eral guidelines for the construction of new facilities. However,
the substantially higher costs associated with firing coal, due
primarily to handling and cleanup operations, discourages manu-
facturers from using it as the principal fuel source. The emis-
sions from an oil-fired furnace would be significantly different
from the values presented in Table 19.
Data on the emissions from the dryer furnace, which fires a
No. 2 distillate fuel oil, can also be found in Table 19. After
contacting the wet grain stream, the moisture-laden air and flue
gases first pass to the dryer cyclone and then to a wet cyclone
scrubber for final removal of particulates. Most of the water
condenses in the scrubber and hence serves as makeup water for
the recirculating scrubber liquor. Based on the operating param-
eters of such a system, the outlet criteria pollutant concentra-
tions were determined to assess compliance with the relevant reg-
ulations . Such regulations for a medium size industrial furnace
(10.5 to 264 million kj per hour) have not yet been developed
under New Source Performance Standards (NSPS). The more strin-
gent standards for utility size furnaces (less than 264 million
kj per hour) were then examined as a guideline. As shown in
Table 19, the scrubber air effluent easily meets each appropri-
ate standard.
48

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TABLE 19. AIR EMISSIONS FOR AN ALCOHOL FACILITY
Stream
Fermentation Vent
co2
Hydrocarbons
Quantity
Generated
kg/hr
6,360
Trace
Ultimate Disposition
Condensed and sold,"
or vented to the
atmosphere
Main Boiler - Coal-Fired
(129 x 106 kj/hr)
Flue Gases:
CO,
N2
°2
N03
SO,
x
Fly ash
Unburned hydrocarbons
(no control applied)
67,550
11,610
3,030
47,820
4,455
40
260
360
7
Requires a mechani-
cal collector/wet
scrubber system
Dryer Furnace - Oil-Fired
(48 x 106 kj/hr)
Flue Gases - Scrubber
Outlet:	107,050
CO2	17,730	Vent to atmosphere
H2	14,200
N2	73,180
02	1,840
S02	6
N0X	2.5
Particulates	0.3
Benzene Fugitive Emissions	NDA
49

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Fugitive,emissions of benzene from the dehydration section
are considered to be minimal if an equipment maintenance schedule
is instituted and proper housekeeping procedures followed.
Was tewater--
Table 20 presents data on wastewater streams generated by
the alcohol facility. The stillage, which includes sludge recy-
cled from the on-site wastewater- treatment" plant, is dried -for
sale as cattle feed. This process not only eliminates a potent
waste stream from the treatment plant but also produces a sale-
able by-product.
The cooling tower blowdown is the largest volume influent to
the treatment plant. This stream carries 63 percent of the total
solids loading; however, only 8 percent of the total BOD load is
introduced by this waste stream. The analysis of this stream
varies widely depending on the makeup water source, the materials
of construction used in the cooling water system, and the process
condensates which are added to the system.
The strength of the evaporator condensate is a strong func-
tion of the type of evaporation scheme used. In this design, the
condensate represents 2 percent and 32 percent of the solids and
BOD loadings, respectively. Although it is a low pH stream
(3.9), the dilution factor is large enough to prevent any acidity
problems for the wastewater treatment plant.
The plant and equipment washes contribute a significant por-
tion to the wastewater system. This stream represents 23 percent
of the total BOD load. This large portion is characteristic of
washes used in any food or grain processing equipment especially
for batch-type vessels. Instruction in conservation-oriented
housekeeping procedures should be conducted to avoid high volumes
of wash waters. Much of this water can be reused after settling
and removal of solids.
Bottom water from the rectifying column, though high in BOD
concentration, is a small volume stream. This stream, as well as
the boiler blowdown and sanitary sewage, contributes only minor
loadings to the treatment plant.
The wastewater treatment system employed is an extended aer-
ation-activated sludge unit. This technology was selected pri-
marily because it reflects current operating practices in the
beverage grade alcohol industry. Mean cell residence times of 20
to 30 days (sludge age with hydraulic retention time of 18 to 36
hours) are typical for this type of unit. Further discussion of
this and other systems may be found in the control technology
evaluation section of this report.
50

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TABLE 20. SUMMARY OF INFLUENT WASTEWATER CHARACTERISTICS

Quantity Generated
Total
Solids
Suspended
Solids

BOD


Stream
kg/day
M'Vday
EE™
kft/day
EES.
kg/day
EES.
kg/day
Z of
Total
Ell
Scrubber Blowdown
300,000
300
2,600
780
760
228
1,040
310
31
5.0
Cooling Tower Blowdown
2,684,000
2,690
800
2,150
14
38
30
80
8
8.0
Boiler Blowdown
65,500
65
100
6
5
0.3
0
0
0
7.0
Evaporator Condensate
492,700
490
130
64
12
6
650
320
32
3.9
Plant & Equipment Washes
349,000
350
1,050
368
400
140
650
227
23
6.0
Rectifier Water
37,150
37
240
9
40
1.5
1,250
46
5
5.0
Sewerage Infiltration
65,500
65
NDA

NDA

NDA


NDA
Sanitary Sewage
43,600
44
750
33
200
9
200
9
1
NDA
Total Wastewater
4,037,450
4,041
843
3,410
104
422.8
246
990
100
NDA
NDA - No Data Available

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Solids-
Solid wastes data are presented in Table 21. Collected fly
ash from the particulate control devices installed with the main
boiler may be in a slurry if a wet scrubber is used, or dry if
mechanical or electrical collectors are employed. This stream
will often be landfilled. Fly ash may be reinjected also. Bot-
tom ash from the main boiler bed is sluiced off into a sedimenta-
tion tank or pond. This material is very coarse and settles
rapidly. The overflow may be discharged without further treat-
ment. The dust from coal handling would either be injected into
the boiler or included with the fly asti for landfill disposal.
The grain dust would probably be recycled to the grain milling
operation. Land disposal of sludges from sanitary sewage and ex-
cess activated sludge will probably continue.
52

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TABLE 21. SOLID WASTES GENERATED
BY AN ALCOHOL FACILITY
Stream
Sludge (effluent from
wastewater treatment)
Power Generation Fly Ash
Bottom Ash - Main Boiler
Collected Coal Dust
Collected Grain Dust
Miscellaneous Plant
Wastes
Quantity
Generated
kg/hr
46
360
195
NDA
NDA
NDA
Ultimate Disposal
Recycled to dryer
Landfilled
Slurried and
ponded on-site or
contracted out;
overflow from pond
discharged
Landfilled
Recirculated
Incinerated or
contracted
NDA: No Data Available
53

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SECTION 4
REVIEW OF ENVIRONMENTAL REGULATIONS
In keeping with the objectives of Task 3 in the Work Plan,
this section identifies the federal and state environmental regu-
lations which may affect the alcohol industry. The results are
utilized to determine the minimum pollution control technology
requirements which are discussed in Section 5, Control Technology
Requirements. The Methodology section contains a discussion of
the methodology selected to analyze the regulations. An analysis
of the applicable regulations according to air, water, and solid
waste is reported in the Air Regulations, Federal Regulations,
and State Regulations sections.
METHODOLOGY
To identify pertinent emission standards and appropriate
pollution control requirements for air, water, and solid wastes
from the alcohol industry, it is necessary to:
•	Characterize the air, water and solid waste streams; and
•	Review federal and state environmental regulations.
Characterization of the waste streams was done in a previous
section of this report and a summary of the results is provided
in the Appendix Table B-1. Also, a summary of the major emission
sources and corresponding pollutants based on the calculations in
Section 3 is given in Table 22.
Federal and state environmental laws were reviewed for regu-
lations specific to the alcohol industry as well as for major
emission sources and pollutants produced in an alcohol facility.
Implementing regulations for the following federal environmental
laws were reviewed: the Clean Air Act of 1970 as amended through
1977; the Water Pollution Control Act Amendments of 1972 (as
amended by the Clean Water Act of 1 977 and other amendments
through 1978); the Resource Conservation and Recovery Act of
1976. Air, water, and solid waste regulations promulgated by the
states of Colorado, Illinois, Iowa, Kansas, Missouri and Nebraska
were reviewed. These states were chosen because they either pro-
duce or have plans to produce alcohol for "blending in Gasohol in
the near future. Also, regulations from other states considering
alcohol production were reviewed to confirm that the above
states' emissions standards for the alcohol industry are repre-
sentative.

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TABLE 22. ALCOHOL PLANT WASTE STREAMS
AIR EMISSIONS
Stream	kg/hr
Main Boiler Flue Gases	67,550
NO__	40
A
S02	260
Fly Ash	360
Unburned Hydrocarbons	7
Coal Dust	NDA
Grain Dust	NDA
Dryer Flue Gases	92,840
N°x	3
S02	6
Particulates	32
Fermentation Vent
C02	6,360
Hydrocarbons	NDA
Fugitive Emissions	NDA
WASTEWATER
Influent to Wastewater Treatment	168,180
Scrubber Blowdown	12,400
Cooling Tower Blowdown	111,800
Boiler Blowdown	2,730
Evaporator Condensate	20,590
Plant & Equipment Washes	14,550
Rectifier Water	1,550
Sewerage Infiltration	2,730
Sanitary Sewage	1,820
(continued)
55

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TABLE 22.(continued)
WASTEWATER
(continued)	kg/hr _
Total BOD	226 ppm
Total Solids	843 ppm
Total Suspended Solids	104 ppm
SOLID WASTE
Sludge from Biological Treatment	46
Power Generation
Fly Ash	360
Bottom Ash	195
Dust (Coal & Grain)	NDA
Plant Wastes (boxes, trash, etc.)	NDA
NDA - No Data Available
56

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Air Regulations
After reviewing the Clean Air Act and its amendments, the
Standards of Performance for New Stationary Sources, and the ap-
propriate states' air regulations, it was found that there are no
air regulations which specifically address the fermentation alco-
hol industry.
Table 22 and Table B-1 show that the major potential sources
of air pollution will be the following:
•	Criteria pollutants from combustion processes (steam gen-
eration, process heaters);
•	Dust from coal handling and grain drying;
•	Organic vapors from fermentation vent; and
•	Uncondensed organics from distillation overheads, flash
cooler, and evaporators.
Fugitive emissions of benzene and other volatile organics
may also be a potential source; however, if proper maintenance
and housekeeping procedures are followed, these emissions will be
small.
Emission standards do exist for sources such as fossil fuel-
fired steam generators, incinerators and grain elevators; these
generic standards will probably be applied to this equipment as
it is found in the alcohol industry. General emission standards
which may potentially affect the industry will also be applied to
particulate matter and sulfur dioxide generation. Pertinent fed-
eral and state regulations are addressed in detail in the para-
graphs below.
Federal Regulations--
Table 23 gives the specific federal standards of performance
for fossil fuel-fired steam generators, incinerators, and grain
elevators. These are the only sources of air emissions found in
the alcohol industry which fall under federal regulation. These
standards are applicable unless superseded by more stringent
state regulations.
Other federal regulations or standards which could affect
the degree of emissions control required include the maintenance
of National Ambient Air Quality Standards (NAAQS) which are sum-
marized in Table B-2. Compliance with Prevention of Significant
Deterioration (PSD) requirements is also necessary. The PSD reg-
ulations include both an ambient air increment analysis, present-
ed in Table B-3, and a control technology review which requires
57

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TABLE 23. EPA AIR REGULATIONS ON STANDARDS OF PERFORMANCE
FOR NEW STATIONARY SOURCES
Emission Standards
Source
Fossil-Fuel-
Fired Steam
Generators
Incinerators
Grain
Elevators
(2)
Applicability
<264 x 106 kj/hr
Heat Input
45,450 kg/day
Dryers
Any Process
Emission
Truck or Railcar
Unloading
Station
Railcar Loading
Station
Truck Loading
Station
Any Grain Hand-
ling Operation
Particulate
Matter
0.05 kg/106 kj
0% Opacity
0.02 g/M3
(07. Opacity)
5% Opacity
5% Opacity
107. Opacity
07. Opacity
so.
0.38 kg/10 kj
(liquid fuel)
0.58 kg/106 kj
(solid fuel)
0 18/M
3 (1)
NO
X
0.14 kg/106 kj
(liquid fuel)
0.34 kg/106 kj
(solid fuel)
(1)	Corrected to 12 percent COj.
(2)	There are also particulate emission standards for barge or ship loading and unloading
stations which have not been listed here.

-------
best available control technology for major sources of pollution..
For a particular alcohol plant to be classified as a major
stationary source under the PSD regulations, it must emit, or
have the potential to emit, 250 tons or more per year of any air
pollutant regulated under the Clean Air Act and its amendments.
State Regulations--
- ¦ The flue gas from—the fossil"" fuel-fired steam generator' is
the largest single source of air emissions from an alcohol plant.
Table 24 presents a summary of the required fuel combustion
emission standards of each chosen state as a function of the
actual heat input. A more detailed account of air regulations
for the states can be found in Table B-4 of the Appendix.
Another major source of particulate matter emissions stems
from grain handling and drying. Illinois and Iowa have specific
regulations governing emissions from these sources as shown in
Table 25. Particulate emissions from grain handling and drying
for the other four states will be controlled by the most strin-
gent of -the following - regulations : Particulate Emission Stan-
dards for Process Emission Sources (Table B-5) and/or State Air
Regulations for Fugitive Dust and Ground Level Particulate
Concentrations (Table B-6).
In addition to the grain handling and~ drying air emissions,
the particulate matter emission requirements listed in the above
tables will also regulate particulate emissions from any other
process or fugitive emission source. Table 26 gives particulate
emission requirements for incinerators and emission limitations
for volatile organic compounds in the states of Colorado and Il-
linois .
Finally, it should be noted that the National Ambient Air
Quality Standards or the states' ambient air quality standards
(Table B-7), if more stringent than any of the above regulations,
must be maintained at all times.
Water Regulations
As with air emissions, no specific regulations which govern
the waste stream effluents for the alcohol industry were found.
Table 22 and Table B-1 show that the major volumes of wastewater
are from the process condensates and the cooling water blowdown,
while the major pollutants of concern are organic suspended
solids. An analysis of the stillage that forms the major com-
ponent of these organic solids appears in Table B-8.
Federal Regulations--
Although no federal effluent guideline_s have been established
for the alcohol industry, effluent guidelines and standards do
exist for grain mills and sugar processing if either of these
operations takes place on-site. However, because they do not
59

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TABLE 24. SUMMARY OF STATE AIR REGULATIONS FOR FUEL BURNING EQUIPMENT^
Ringlemann
Particulate
Emissions
(kg/10 k.1)
(2)
Sulfur Dioxide
Emissions
(kg/106 kj)
State
Opacity
Chart
Coal
Oil
Coal
Oil
CO
20

0.07
0.07
0.6
0.9
IL
30

0.05
0.05
0.9
0.5
IA
40
2
0.29
0.29
2.9
1.2
KS
20

0.16
0.16


MO
20
1
0.12
0.12
3.8
3.8
NB
20
1
0.16
0.16
1.2
1.2
(1)	Specific air quality zones exist within each state which might mandate
different emissions requirements (see Table B-4).	g
(2)	Basis for emission standards is a heat input of roughly 132 x 10 kj.

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TABLE 25. SUMMARY OF STATE AIR REGULATIONS FOR GRAIN HANDLING AND DRYING
State
X Particulate Removal Required
Throughout
(35.300 M /Yr)
Cleaning &
Separating
Major Dump
Pit Area
Interna]
Transferring
Area
Load-Out
Area
Dryers
Allowable
Particulate
Emissions
(mg/M )
Illinois
(1)
<2
>2
90
98
90
98
90
98
90
98
90
98
Iowa
(2)
Any
0.23
O
(1)	These regulations do not apply to grain annual throughputs of less than 10,590 M .
(2)	For, any grain handling or processing, 0.1 graln/SCF Is the maximum amount of particulate matter
allowed In the exhaust gas.

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TABLE 26. STATE AIR REGULATIONS FOR INCINERATORS
AND VOLATILE ORGANIC MATERIAL
Volatile Organic Haterlal
IL
IA
KS
MO
NB
Incinerator
Storage
Emissions Criterion
State
CO
New or
Existing
Sources
New
Existing
Either
All
Sources
Remaining
Existing
Sources
Remaining
New
Sources
All
Sources
All
Sources
All
Sources
All
Sources
Chsrge Rate
(kg/lir)
Any
Any
Any
910-27.270
>27,270
<450
>450
<90
2,730
>2,730
<90
^90
<910
>910
Particulate
Emissions
(g/H )
0.23
(1)
0.35
0.35
0.18
0.12
0.46
0.23
0.81
0.46
0 69
0.46
0.23
0 69
0.46
0.46
0.23
(?)
(3)
Capacity
(M )
Control
Efficiency
Z
152
85-90
Emissions
Condition
lleated In
Presence
of Oxygen
Any Other
Any
A1lovable
Emissions
(kg/day) (kg/lir)
c.a
18 2
1.4
3.6
3.6
Z
Removal
Required
85
85
(4)
(1)	Effluent gases are corrected to 12 percent dioxide.
(2)	Emission limitations foi Incinerators In designated air pollution control areas.
(3)	Emission limitations for Incinerators outside designated air pollution control areas.
(4)	Emissions of organic material In excess of those shown are allowable If such emissions are controlled by
one of the following methods; (a) Flame, thermal or catalytic Incineration so as either to reduce such
emissions to 10 ppm equivalent methane (molecular weight 16) or less, or to convert 85 percent of the
hydrocarbons to carbon dioxide and water; or (h) A vapor recovery system which adsorbs and/or absorbs
and/or condenses at lent>t 85 percent of the total uncontrolled organic material that would otherwise be
emitted to the atmospheie; or (c) Any other air pollution control equipment approved by the Agency capable
of reducing by 85 percent or more the uncontrolled organic material that would be otherwise emitted to the
atmosphere.

-------
apply directly to the alcohol industry, these regulations have
not been included in this report.
Secondary treatment of industrial wastes may be required if
the wastes are discharged into navigable waters and contain bio-
chemical oxygen demand (BOD) and suspended solids (SS). Since
many alcohol production waste streams are high in BOD and SS,
secondary treatment~ "as ~ a~ minimum," will probably be required.
Federal effluent standards for secondary treatment are shown in
Table 27.
If an alcohol facility uses a publicly owned treatment works
(PGTW) for disposal of its wastes, pretreatment of the wastes
will almost certainly be required. Specific pretreatment stan-
dards depend on waste characteristics and POTW requirements.
Therefore, only the following general pretreatment requirements
can be given:
•	No pollutants which create fire or explosion hazards may
be - discharged to-a POTW;
•	No discharge which will cause corrosive structural dam-
age--no discharges with pH less than 5.0;
•	No solid or viscous pollutants discharged in amounts
which will cause obstruction to the flow in sewers;
•	No discharges of any pollutant, including oxygen demand-
ing pollutants (BOD, etc.), released in a discharge of
such volume or strength as to cause interference in the
POTW; and
•	No discharges of waste heat in amounts which will inhibit
biological activity in the POTW that result in interfer-
ence; in no case will heat be discharged in such quanti-
ties such that the temperature at the treatment works
influent exceeds 40°C (104°F) unless the works is
designed to accommodate such heat.
Only the latter two provisions are areas of potential concern for
an alcohol facility.
Notwithstanding any of the above regulations, the EPA ad-
ministrator can establish effluent limitations for a source or
sources interfering with the attainment or maintenance of any
promulgated water quality standards.
State Regulations--
In reviewing the state water regulations, none were found
specific to the alcohol industry. Table 28 lists the effluent
limitations for BOD, SS, and pH for the states reviewed. All of
these emissions limitations are directly applicable to the
63

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TABLE 27. FEDERAL EFFLUENT QUALITY STANDARDS
FOR SECONDARY TREATMENT

BOD
(mR/1)
(tng/1)
pH
30-Day Average
30
30
6-9
7-Day Average
45
45
6-9
Percent Removal Efficiency
85
85
	
Required (30-Day Average)
64

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TABLE 28.
SUMMARY OF STATE WATER REGULATIONS POTENTIALLY
GOVERNING THE ALCOHOL INDUSTRY
State
Colorado
Illinois
Iowa
Kansas
Missouri
Nebraska
(2)
(3)
Control
Technology
Required
BMP
BUT
BMP
BPCT
BPCT
BPCT
Discharging^ ^
To Public
Facilities pH
Pretreatment 6-9
Required
Pretreatment 5-10
Required
Pretreatment
Required
Pretreatment 6-9
Required
Pretreatment
Required
Pretreatment
Required
Effluent
Criteria
SS (mg/1)
BOD
(mg/1)
7-Day 30-Day 7-Day
Average . Average Average
45
45
30
37
30
30
45
45
30-Day
Average
30
30
30
30
Removal
Required
SS B0Dc
85 85
85
85
85
85
85
85
85
85
(1)	Pretreatment criteria are governed by EPA's Pretreatment Standards (40 CFR 128) and by specific
public treatment works requirements in order to meet effluent limitations and/or water quality
standards.
(2)	No more than 5 percent of the samples collected shall exceed 2.5 times the numerical limits pre*
scribed by this rule.
(3)	The 85 percent reduction requirement for SS and BOD,, was not specifically stated in Missouri's
regulations. This is the degree of control expectea to be required and represents BPCT for this
type of facility.
NOMENCLATURE: SS = Suspended solids
BMP = Best management practices
BDT = Best degree of control
BPCT = Best practical control technology
BOD,. = 5-Day biochemical oxygen demand

-------
wastewater being generated at an alcohol plant. It can be seen
that an 85 percent reduction in BOD and SS is required.
As was previously stated in the federal regulations, pre-
treatment standards for effluents discharged to a POTW are de-
pendent upon the wastes being discnarged and the specific re-
quirements of the POTW.
In all cases, the state water quality standards must be
maintained. Therefore, emission limitations can be set by the
state for any pollutant for which there is a water quality
standard and the commensurate emission reduction required can be
more severe than the amounts mandated at the federal level.
Solid Wastes Regulations
The major components of the solid wastes generated at an
alcohol plant which fires coal are bottom ash from the main
boiler; fly ash, coal dust, and grain dust from particulate con-
trols; and wastewater sludge containing organic species such as
protein, oils, starch, and yeast. The sludge may also contain
traces of ethanol, fusel oils, and pesticides. At this time, the
levels of pesticides present in the solid wastes is unknown. It
is expected, however, that the pesticides will be present at the
ppb level.
Federal Regulations--
It is believed that most distillers will dispose of less
than 100 kilograms (220 pounds) per month of hazardous wastes
(including benzene and pesticides). In this event, they must
comply with Section 250.29 (persons who dispose of less than 100
kilograms per month of hazardous waste, retailers, and farmers)
of the proposed Resource Conservation and Recovery Act regula-
tions. In general, this provision requires that any hazardous
waste generated, no matter how small the quantity, be disposed of
either in:
•	A solid waste facility which has been permitted or other-
wise certified by the state as meeting the criteria pur-
suant to Section 4004 of RCRA; or,
•	A treatment, storage, or disposal facility permitted by
the administrator pursuant to the requirements of Section
3005 (Permits for Treatment, Storage, and Disposal of
Hazardous Waste), or permitted by an authorized state
program pursuant to Section 3006 (Guidelines for Autho-
rized State Hazardous Waste Programs) of RCRA.
State Regulations--
No specific regulations were found for disposal of industri-
al solid wastes from the alcohol industry. The following general
requirements were given for disposal of solid wastes for all the
states "reviewed-
66

-------
•	Permit to construct disposal site required:
Site selection has to be approved
Engineering design criteria for site have to be met
•	Permit to operate is required:
Operating plans and processing facilities design and
operation must meet specific criteria and be approved-
Site and facilities are to be inspected before opera-
tion can commence
•	Regulations developed for storage and transportation of
wastes;
•	Special operating permit (or approval) is required for
disposal of hazardous wastes; and,
•	Sites must be environmentally sound; they must be de-
signed to comply with all air and water laws (or any
other environmental regulations that would apply).
67

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SECTION 5
CONTROL TECHNOLOGY REQUIREMENTS
In this section, alcohol process effluent streams are com-
pared with environmental regulations to determine the environmen-
tal control requirements necessary for alcohol plants which would
support a large-scale Gasohol industry. These control requxre-
ments are defined in terms of the component to be controlled,
level of control required, and the source and characteristics of
the stream to be controlled. Control options are identified with
an emphasis on alcohol plants which utilize grain as a feedstock
and employ coal-fired boilers for power. The criteria which are
used to evaluate the control options are:
•	Development Status;
•	Applicability;
•	Performance;
•	Capital Cost and Operating Cost; and
•	Secondary Pollutants.
AIR EMISSIONS
As mentioned in Section 4.2, the major sources of air pollu-
tion from an alcohol plant are:
•	Criteria pollutants from combustion processes (steam gen-
eration, process heaters);
•	Dust from coal handling and grain handling and by-product
drying;
•	Hydrocarbon emissions from fermentation vent, distilla-
tion overheads, flash cooler, evaporators, storage; and
•	Fugitive air emissions.
Criteria Pollutants
Combustion of fossil fuels such as coal or oil to provide
the relatively large amount of energy used in alcohol production
68

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results in significant quantities of criteria pollutants such as
N0X, SC>2, and particulates. Table 29 illustrates the levels
of these pollutants when a No. 6 Illinois coal is used in a
coal-fired boiler.
Federal new source performance standards (NSPS) currently
apply only to combustion sources having gross heat inputs greater,
than- 264-x 10^ k j - per - hour-, a level -somewhat larger tnan~-~ex—
pected in alcohol plants. However, EPA is currently preparing
proposed NSPS for smaller sources (industrial boilers).
A comparison of the estimated air emissions in Table 29 with
the state regulations (Table 24) reveals the following:
•	N0X is not a major problem (no N0X) standards were appli-
cable for the states examined);
•	SC>2 control is needed in Colorado, Illinois, Ne-
braska; and,
•	Particulate control up to 98.5 percent removal is needed
in all states.
In situations where N0X control is necessary, there are
two general - methods of control for large stationary sources:
combustion modifications and flue gas treating (FGT). Presently,
combustion modifications are commercially available technology
while FGT technology is just emerging from the developmental
stages. Although FGT control is more efficient, it is also more
expensive. Combustion modifications such as staged combustion,
flue gas recirculation, and low air firing, which reduce NGX
emissions by about 30 percent, should be sufficient for N0X
control.
Flue gas desulfurization (FGD) is a technology for the re-
duction of SC>2 emissions from coal or oil combustion. Although
there are several processes termed regenerable which are reaching
commercialization, throwaway systems (where sulfur is disposed in
a landfill or ponded) are more common; only throwaway systems can
be commercial in terms of regular application to non-prototype
systems.
The installation of FGD equipment on coal-fired boilers in
alcohol plants is highly unlikely due to high capital cost and
operating expenses, secondary pollution, and availability of
low-sulfur coal or fuel oil. The capital cost of a lime/lime-
stone system for the conceptual alcohol plant (probably the least
expensive control option), is estimated to run from 5 to 10 mil-
lion dollars, or about 25 percent of the cost of the rest of the
alcohol plant. Also, the operating expenses may cost the
distiller about $.03 per liter ethanol, which does not include
69

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TABLE 29. BOILER EMISSIONS AND ENVIRONMENTAL
CONTROL REQUIREMENTS
Uncontrolled
Boiler
Emissions
(1)
SO,
(2)
(kg/hr)
260
Particulate
Matter
(kg/hr)
360
(3)
State
Permissible
Emissions
(kg/hr)
% Removal
Required
Permissible
Emissions
(kg/hr)
% Removal
Required
Colorado
68
74.0
8.0
97.9
Illinois
103
61.1
5.7
98.5
Iowa
341
0.0
34.0
90.8
Kansas


18.7
94.9
Missouri
455
0.0
14.2
96.2
Nebraska
142
46.0
18.7
94.9
(1)	Basis 132 MM kj/hr heat input; using Illinois No. 6 coal with heating
value = 5,610 kj/kg, 2.7% S, 11.7% ash.
(2)	All S in coal assumed to form S0_.
(3)	Sixty-five percent of ash in coal is converted to fly ash for a Spreader
Stoker Boiler.
70

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the cost of sludge disposal. The throwaway systems such as the
lime or limestone processes generate sludge that must be disposed
of in ponds or in landfills. Leaching from these disposal sites
can potentially pollute ground or surface waters. Finally, the
use of low-sulfur coal that exists in western states which have
the most strict SO2 regulations would make FGD unnecessary.
Fuel oil might be an alternative in other areas where low-sulfur_
coal might' be unavailable.
A comparison of environmental regulations with the flue gas
emissions from a coal-fired boiler reveals that particulate con-
trol (fly ash) will be a major problem for the distiller. Many
control devices exist for controlling particulate matter, such as
fabric filters (baghouses), wet scrubbers, electrostatic precipi-
tators (ESP), and inertia! separators. Table 30 presents a brief
characterization of each of these control options. In most
applications, inertial separators (which include impingement,
cyclone, or mechanical centrifugal separators) will not be effi-
cient enough to be considered, except as pre-collectors to con-
trol devices which can remove fine particulates.- Electrostatic
precipitators will also be uncommon in alcohol production facili-
ties due to their high capital cost. Wet scrubbers will provide
adequate control for some states,-but might be avoided due to the
large quantities of liquid waste generated by these control de-
vices. Therefore, baghouses are probably the best alternative
for particulate control from coal-fired boilers when high effi-
ciency removal is necessary.
Dust from Coal Handling, Grain Handling, and By-Product Drying
The handling of coal and grain, as well as by-product drying
(DDG production) will pose another particulate control problem
for the distiller. The control options for these particulates
are similar to those for fly ash particulate control. Use of
ESP's and wet scrubbers has been limited in existing facilities
due to high cost, explosion hazards, and desirability of having a
dry by-product.
Though cyclones are very common in grain handling indus-
tries, only low or medium efficiency separators are used due to
the increased operational cost and maintenance associated with
high-efficiency multiple cyclones. In many cases, cyclone ex-
hausts are routed through filter cloth to remove fine particu-
lates. Baghouses (using cotton sateen) are ideal for areas with
strict regulations for particulate control and should be used on
all systems except by-product drying.
Wet scrubbers are the best alternative for exhaust gases
from direct-contact DDG dryers because these dryer particulates
will easily cake on fabric filters and severely decrease their
71

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TABLE 30. PARTICULATE MATTER CONTROL OPTIONS
Development
Status
Applicabil-
ity
Performance
Capital
Cost (3)
Operating
Cost
Secondary
Pollutants
Fabric
Wet
Electrostatic
Inertial
Filters
Scrubbers
Precipitators
Separators
Commercially
Commercially
Commercially
Commercially-
available,
available,
available,
available,
widely used
widely used
widely used
widely used
Excellent for
Extensively
Standard con-
Most widely
collection of
used for pro-
trol devices
used partic-
fly ash and
cess and
for the elec-
ulate matter
dust from
combustion
tric utility
control
coal hand-
sources
industry (2)
devices; ade-
ling (1)


quate for



controlling



dust from



materials



handling and



fly ash
High effi-
>95% effi-
High effi-
79-90%
ciency
ciency for
ciency
removal effi-
(>99.9),
1 micron or
(>99%) for
ciency, not
90% effi-
smaller
submicron
for fine
cient for

particles
particulate
submicron


control
particles



Relatively
Moderate
Very high
Low
high



Moderate
Relatively
Moderate (5)
Low

high (4)


Solid waste
Liquid waste
Solid or
Solid waste


liquid waste

(1)	Fabric weave and finish can be designed for special applications.
(2)	Submicron particle removal requires very high energy inputs.
(3)	High maintenance cost.
(4)	Collection of very high or very low resistivity particles is difficult.
(5)	All control options are rated on the same basis: 10,000 acfm, 24 C gas
temperature, non-corrosive gas, 7,000-hour operating time, and mid-1977
base data.
72

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effectiveness.. The liquid waste from the wet scrubbers will no.t
pose a disposal problem since it can simply be sent to wastewater
treatment.
Hydrocarbon Emissions
Sources of hydrocarbon emissions from an alcohol facility,
(other than from combustion) include the ventS" from:
•	Distillation columns;
•	Flash cooler;
•	Evaporators;
•	Vacuum ejectors; and
•	Fermenters.
Illinois and Colorado are- the- only states which-have regula-
tions governing hydrocarbon emissions from these types of
sources, the latter state requiring 85 percent removal (see Table
25). Since the hydrocarbon streams from the first four sources
are too dilute to be economically recovered and do not have a
high recoverable market value, the simplest and most effective
control for these hydrocarbons would be direct flame incinera-
tion, or flares. Most flares are sized to operate at efficien-
cies between 95 and 99 percent, although higher efficiencies can
be obtained. In the event the emissions are too dilute for di-
rect combustion, the vent streams could be utilized as the air
feed to process burners (e.g., DDG drying). Thus, the distiller
can control these hydrocarbon emissions and at the same time de-
crease fuel requirements.
In many existing alcohol plants, the CO2 stream from the
fermenter, which is more than 99 percent CO2 and water vapor
with traces of organics, is vented to the atmosphere. Although
not a significant source of pollution, modern distillers may pre-
fer to collect and condense the CO2 since a good market cur-
rently exists. If a distiller chooses to recover CO2, all im-
purities can easily be removed from the CO2 stream prior to
cryogenic recovery by passing the vent gas through a water scrub-
ber to condense the water vapor and any organic vapors present in
the CO2 stream. The blowdown from the water scrubber can be
routed to wastewater treatment.
As shown in Table 26, the State of Illinois requires that
volatile hydrocarbon emissions (i.e., alcohol emissions) from
storage facilities of 150 (40,000 gallons) or more must be
controlled by 85 to 90 percent. Since this quantity amounts to
less than 1 day's production, compliance must be maintained by
73

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the distiller. Floating roofs or internal floating covers can
be employed to control storage emissions. These devices reduce
tankage emissions by eliminating the vapor space above the prod-
uct surface. Efficiencies for floating roof tanks and internal
floating covers are 85 and 95 percent, respectively.
Fugitive Air Emissions
Fugitive dust emissions can be caused by several activities-
occurring at alcohol production facilities:
•	Unpaved roads
Personnel and maintenance vehicles
Raw material or waste hauling vehicles
•	Windblown dust
Unpaved, bare ground
Waste piles (bottom ash)
Raw material piles (coal, grain)
•	Materials handling
Front-end loaders, etc.
Conveyer systems.
Control of fugitive dust is aimed primarily at preventing or con-
fining the emissions rather than collecting afterwards. Commonly
used dust control methods are listed in Table 31. In the case of
conveyer controls (confinement by hoods), an induced air flow
draws the entrained dust through a conventional control device
for removal and disposal. The other controls are purely prevent-
ative in nature.
Fugitive hydrocarbon emissions have two principal sources:
leaks and evaporation from open surfaces. Unlike fugitive dust,
which arises in a diffuse way over an area, many fugitive hydro-
carbon losses occur from specific points such as valves or
flanges. However, these sources are so numerous in most plants
processing hydrocarbon liquids that the emissions can be consid-
ered diffuse for practical purposes.
Fugitive hydrocarbons are prevented by maintenance and de-
sign. Consequently, there are no specific recommendations for
their control. The methods below are frequently applicable:
•	Confinement, diversion, and flaring;
•	Dual seals;
74

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TABLE 31. FUGITIVE DUST CONTROL METHODS
Source
Unpaved Roads
Control Method
Reducing Vehicle Speeds
Wetting
Paving
(1)
Control
Efficiency
25-40%
50%
85%
Windblown Dust
Wetting
Confining (Covers or
Enclosures
50%
100%
(2)
Materials
Handling
Wetting
Confining (Hoods over Con-
veyors with Air Pickups
at Transfer Point)
50%
80%
(1)	Because control efficiency is highly dependent on dust
characteristics, meteorological parameters and other
factors, these figures represent only very rough
estimates.
(2)	This control efficiency only applies while the cover is in
place.
75

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•	Sparing of critical pumps, compressors, and valves;
•	Use of surface condensers rather than direct-contact
units (barometric or low-level jet); and
•	Use of outages for repairs and a systematic preventive
maintenance program.
WASTEWATER TREATMENT
The first step in assessing the wastewater control technol-
ogy requirements is to delineate the treatment objectives. Most
of these objectives have already clearly been defined by the
Federal Water Pollution Control Act Amendments of 1972 (Public
Law 92-500) and other state laws. A survey of the applicable
federal and state regulations, previously presented in Section 4
of this report, will provide the framework for identification of
the necessary control technologies.
The next step is to examine the influent wastewater charac-
teristics to determine the degree of treatment required to comply
with existing regulations. A summary of these characteristics
generated from the conceptual design of an alcohol facility is
presented in Table B-1.
A comparison of the pertinent regulations regarding the pol-
lutant loadings shows the necessity for nearly 88 percent removal
of the influent BOD to 30 ppm (30-day average), and 85 percent
removal of the suspended solids. No significant pH problems are
anticipated, but nonetheless, care should be exercised when using
alkali washes for equipment cleanup. Each of the above criteria
will be used to guide the selection of the appropriate control
systems.
It should be noted that dissolved inorganics, primarily from
boiler and cooling water blowdown and the ash sluicing system if
a coal-fired boiler is used, are not specifically regulated; how-
ever, discharges of metal ions which would violate water quality
standards will require control. Also, pretreatment regulations
will require control of toxic substances which could inhibit or
even stop activity in a biological wastewater treatment process.
The levels of these pollutants in wastewater from a distillery
are a function of the following:
•	Makeup water ion concentration;
•	Materials of construction;
•	Degree of ion concentration per cooling or boiler water
cycle; and
76

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• Hydraulic detention time in cooling water or boiler water
cycles.
These parameters vary widely depending primarily on loca-
tion, internal plant water reuse, and other plant operating pro-
cedures. Should these potential pollutants occur in sufficient
amounts, a suitable control technology would be required. How-
ever, past experience in the alcohol industry has shown tfh'ese-
levels to be below the concentration necessitating treatment, and
therefore, no dissolved inorganic control technologies will be
discussed.
Suspended Solids Treatment
The suspended solids are first treated by preliminary
screening and sedimentation for removal of the coarse solids.
This screening often involves the passage of wastewater across an
inclined wedgewire screen. Sedimentation is a general process
usually denoting the gravity settling of the suspended solids in
a holding tank. Air flotation and flocculation are also candi-
date treatment processes for suspended solids reduction, but
these involve higher operating costs due to the requirements for
chemical addition.
The suspended solids portion of the effluent from this pre-
treatment system are mostly volatile and are treated using the
biological oxidation processes outlined in the following section.
The nonvolatile portion is settled in the biotreatment unit with
the biological floe. Final clarification may be necessary to
meet the standard of 30 ppm suspended solids (30-day average) in
the final effluent.
Dissolved Organics
The core of an efficient distillery wastewater treatment
system is the biological oxidation process. Table 32 outlines
the key operating parameters of four possible classes of bio-
treatment processes which might be implemented in an alcohol
facility. Some of the specific treatment processes might not
provide sufficient BOD removal, which is the primary selection
criterion. Obviously, the capital and operating costs will also
form important selection criteria for the alcohol producer; these
vary widely and hence are described only qualitatively in this
table. A short description of each treatment process likely to
be included in a future fuel alcohol wastewater treatment system
follows.
Existing facilities are often equipped with either a high
rate trickling filter system or an extended aeration activated
sludge unit. Associated with the former is a reasonable resist-
ance to shock loading and an ability to process consistently high
77

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TABLE 32. OPERATING PARAMETERS OF WASTEWATER TREATMENT SYSTEMS
rkDU.ba
Hkui c«1I	Uydruultt	fuud to Hlciu-	VoluM.irlc
Rum JJimt-a	RaleudiMl	oigMtlaa Bolio	loudjng	fiUM	bli
10- 36
0 2-0 4
0 2-0 6
I 5-5 0
0 2-0 6
0 3-0 6
0 fl-2 0
I 2-2 4
1 0-1 2
0 25-0 5
0 25-1 0
0 05-0 15
0 25-1 0
BV95
HS-95
60* 75
00-90
Pui*r
liUUkl
~ uli
hull
Auruted I uAuuiih
Nut A|)|>I1luI)Ic None
Ttiaili.K Hltc»
Low lalii
lllgli rule
liiiorgiiliuiK
SiuunliliiD
Cuiit lllUOUM
SJuugblng
0 OH-O 41
0 41-4 a
Alwjyh
BU-U5
65-tlO
hull
fca«-<.l I cut
IU*I»
4 A»uu»oblc OlRLBiluU
I 6-6 4
ku Vbt>/i»1 J
Ikidciau Kiikruit.
(1)	Cuac«ct unit
(2)	Solids scablllzacloo unit

-------
organic loadings. Recently, concern over the effluent quality
from a trickling filter has caused some operators to construct an
extended aeration unit.
The microorganisms in extended aeration operate in the en-
dogenous respiration phase, during which the substrate for bio-
logical activity includes cellular protoplasm in addition to di^Sr,
solved organics in the~wastewater.~ This'results in "a" more highly
polished effluent with good settling properties. The long reten-
tion times involved limit this system to wastewater flows of
about 1 million gallons a day. Only small volumes of sludge are
wasted; this material can be recycled for drying and inclusion in
the by-product animal feed, landfarmed or used as fertilizer.
For a more detailed discussion of these processes refer to Waste-
water Engineering: Treatment/Disposal/Reuse.
Another alternative to wastewater treatment is to omit by-
product stillage drying and route this waste stream along with
other high BOD and SS waste streams (i.e., flash cooler condens-
ate, rectifier bottoms, and- solvent-recovery bottoms) to an anae-
robic digestor. In practice, the streams are usually concentrat-
ed using centrifugati'on; the thin liquids are recycled to the
cooker or fermenter. Since the resulting waste stream has a
relatively high concentration of solids, it is considered a solid
waste stream and will be discussed in a later section.
An aerated lagoon is also a candidate treatment process for
plant wastes. This option differs from extended aeration primar-
ily because no sludge is recycled. Proper operation of the
lagoon is required for prevention of odors and leaching of harm-
ful pollutants.
The primary difficulty of control technology assessment for
industrial wastewater systems is the wide variability in the in-
fluent wastewater characteristics. Pilot plant studies are al-
most always required for a design suitable for a particular ap-
plication. However, a combination of the technologies discussed
above in a complete system could be designed for compliance with
the pertinent regulations.
SOLID WASTE TREATMENT AND DISPOSAL
Several types of solid or semi-solid (i.e.,' sludge) wastes
will be generated from alcohol production facilities. Some are
directly produced in the alcohol process while others are formed
in power generation when coal-fired boilers are utilized. These
solids include:
•	Power generation bottom ash;
•	Power generation fly ash from particulate controls;
79

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•	Grain dust from particulate controls on grain handlings
•	Coal dust from particulate controls on coal preparation
and/or pretreatment;
•	Wastewater treatment sludge - biological system; and
•	By-product stillage.
Treatment and land disposal of these wastes must be carried
out in an environmentally acceptable fashion to prevent contamin-
ation of surface and ground waters.
For bottom ash and fly ash, landfill is the best disposal
technique available to the distiller. Special precautions must
be taken to ensure that the water table is below the landfill
site. Also, in some cases, provisions must be made for leachate
collection and treatment to avoid contamination of ground waters.
Other particulates from an alcohol plant include grain dust
from grain handling and milling and coal dust from coal handling
and pulverizing. The grain dust collected can be recycled to
grain milling operations and will not present a disposal problem
for the distiller. Likewise, coal dust can be routed to the
boiler and burned as fuel to eliminate this source of solid
waste.
The sludge from biological wastewater treatment in an alco-
hol plant can be converted to a valuable by-product such as fer-
tilizer or animal feed. Techniques available to the distiller
for sludge processing include:
•	Centrifugation and drying;
•	Drying beds; and
o Landfarming.
Since the sludge from wastewater treatment is innocuous, it
is possible to return it to the dryer for DDG production. The
sludge is centrifuged first to remove excess water; the superna-
tant is returned to wastewater treatment. This scheme eliminates
a solid waste disposal problem while increasing the yield of a
valuable by-product.
Drying beds, which consist of filtration media made of sand
and gravel, are the most widely used sludge dewatering method in
the United States. Water is removed by evaporation or drainage
(the collected filtrate is usually returned to the treatment
plant). The method should be restricted to well-digested sludge
since raw sludge is odorous, attracts insects, and does not dry
80

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satisfactorily when applied at reasonable depths. Climatic con-
ditions such as precipitation rate, air temperature, humidity,
and wind velocity are very important in determining effective-
ness. The dewatered sludge is removed mechanically or manually
and can be used as fertilizer.
Landfarming involves applying the wastes in the soil of. a
properly engineered site and using the microbes naturally present
in the soil to decompose the organic fraction of wastes. It i-s
an effective sludge disposal method when pollution preventative
practices are exercised. Application rates, soil conditions,
water runoff, percolation, and odor must be monitored and con-
trolled. Rototillers are usually employed to till the soil to
obtain maximum dewaterability and aeration. This method is par-
ticularly advantageous if large land area is located in proximity
to the alcohol plant.
Much research is currently underway to develop new approach-
es to fermentation by-product processing. One process under in-
tensive investigation is anaerobic digestion of the wet by-prod-
uct stillage. One reason this process is of interest is that
methane produced from this reaction could provide a significant
portion of the plant's energy requirements. Further, speculation
has been made that the market for the dried by-product (DDG) may
diminish as the number of alcohol plants substantially increases.
Anaerobic digestion would provide an additional incentive for
fuel alcohol producers because of the assurance of an on-site use
for a produce whose supply, in the advent of a large-scale Gaso-
hol industry, might otherwise far exceed the demand. The digest-
ed sludge from this control option can be used as cattle feed or
fertilizer.
81

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SECTION 6
SAMPLING AND ANALYTICAL REQUIREMENTS FOR AN ALCOHOL FACILITY
To determine the sampling and analytical requirements neces-
sary to conduct an environmental characterizaiton of a fermenta-
tion ethanol plant, the following steps must be taken:
•	Identification of characterization objectives;
•	Process analysis;
•	Sampling procedure review and- selection;
•	Analytical procedure review and selection, and
•	Identification of data evaluation requirements.
CHARACTERIZATION OBJECTIVES
The objectives of an environmental characterization of an
alcohol plant are:
•	To delineate the identities of pollutants in the gaseous,
liquid and solid waste streams;
•	To determine the	effectiveness of environmental control
modules; and
•	To characterize	selected internal process streams which
affect the plant	emissions and effluents.
To satisfy the first objective, an effluent characterization
must be completed. This entails the measurement of one or more
pollutants in one or more of plant effluent streams.
To address the,second objective, a control module character-
ization must be conducted which investigates the operating per-
formance of one or more pollutant control elements. The charac-
terization test involves sampling both the input and the effluent
streams of selected modules.
To fulfill the third objective, process module characteriza-
tions must be completed. These characterizations carry the
stream analysis at least one module further back into the process
82

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than the control module. Process module characterization defines
the effect of analytical and process parameters of process mod-
ules on the performance of control modules.
PROCESS ANALYSIS
A thorough analysis of process equipment and operating,
parameters is required' for accuracy and efficiency"in determining
the sampling and analytical requirements. The process streams
which should be investigated and the analytical parameters which
should be measured are presented in the paragraphs below along
with the criteria for their selection. A portion of the informa-
tion considered in this review may differ from one alcohol facil-
ity to the next; therefore, the general requirements presented
here will require modification according to a site-specific pro-
cess analysis.
To conduct an environmental characterization of an alcohol
plant, the selection criteria for plant process streams should
include:
•	The objectives of the characterization;
•	The pollutants present; and
•	Material balance considerations.
For the most part, the selection of analytical parameters is
based on regulatory considerations. Two general types of regula-
tions determine the pollutants to be analyzed: pollutant dis-
charge limitations and ambient pollutant standards. Such regula-
tions may exist at the federal, state or local levels, and will
not necessarily be identical. Consequently, regulations appli-
cable to the specific location of an alcohol plant should be re-
viewed when selecting analytical parameters. A summary of ap-
plicable state and federal environmental regulations for fermen-
tation ethanol plants is presented in Section 4 of this report.
Other criteria which are also important are:
•	The need to close material balances for chemical species;
•	The need to analyze for materials which have adverse ef-
fects on control modules; and
•	The usefulness of some analytical parameters as sensitive
indicators of control or process module performance.
A process description of the fermentation alcohol plant is
presented in Section 3, Alcohol Process _Evaluation. The major
processing units are:
83

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•	Milling, cooking, and fermentation;
•	Distillation and dehydration;
•	By-product processing";
•	Steam production; and
•	Environmental control systems.
The emissions and effluent sources from these processes are
discussed below and summarized in Table 33.
Hilling, Cooking, and Fermentation
Gaseous emissions from these processing steps include grain
dust from handling and the vented stream(s) from fermentation,
which often include carbon dioxide and low concentrations of eth-
anol, aldehydes, and water. Liquid effluents typically generated
are wash waters (which are alkali -and high in biodegradable "or-
ganic compounds) and condensate from flash cooling equipment.
Residual pesticides from washing of the grain during handling and
processing could be present. Collected grain dust forms the only
significant solid waste generated from these processing steps.
Distillation and Dehydration
Air emissions from the distillation/dehydration sequence
will include fugitive emissions, noncondensables (CO2, N2,
O2, etc.) and light hydrocarbons from the vents on condensers.
Bottoms from the rectifying and dehydration columns make up the
liquid effluents for this p essin sequence. These streams
have a high biochemical oxygen demand (BOD) and could also be
contaminated with benzene. No solid wastes are directly associ-
ated with distillation and dehydration.
By-Product Processing
Dryer flue gases are the major source of air emissions for
by-product processing if direct contact dryers are employed. The
components of these gases are highly dependent on the type of
fuel fired in the combustion furnace associated with the dryer.
Generally, criteria pollutants (S0X, N0X> particulates, un-
burned hydrocarbons, CO, ozone) might be present, although some,
especially ozone, will be very low in concentration. Liquid ef-
fluents requiring treatment include condensate from the evapora-
tor and wash waters from the various units used in this drying
section. No solid wastes are generated from by-product process-
ing since all can be incorporated into the. by-product distiller's
dried grains.
84

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TABLE 33. EMISSION AND EFFLUENT SOURCES
Section of Operation
Caaecua Einlaalona
	Liquid Effluenta
Solid Wautea
Hilling, Cooking
and FeratenLalTon
00
Ln
UlaL111aLIon und
Dehydration
lly-product Froceaalng
iiteaiu I'toilucL Ion
Envl rooinenlal
Contiol Syatciu
mechanical collectors for milling
operations (|>uriIculatea)
(ciiminui Un venta (CO^ .
Iiydiocurbona)
condenaer vents on coliuuna (benzene
and other volatile organlca)
dryer flue gaaea (HO, SO2, CO,
liydrocaibona, |>aillciiialea)
baioiueLrlc and evaporator condenaer
vents (hydrocarbons)
flue guaea (N<>„, SO2, CO,
|>ui L I culatea)
eva|>oiatlou from biological
lieatment ponda (benzene and
oilier organlca)
waali uateia (dlaaolved
and-suspended solids,
organlca, peaLlcldea,
alkala I)
flaab cooling coiuleuaaLe
(dlaaolved and suspended
solids, oigunlcs)
rectifier bo noma
(organ lea)
dehydration bo t Ionia
(bciuene and other
organlca)
evaporator condensate
(dlaaolved and suspended
ao I Ida , organl i:a)
-	ululcltig ayalema
(Inoigunlcu)
-	boiler hlowdoun
(Inoiganlcs)
-	cooling ual ei blowiloun
(dlsuulved and SUbpeuded
solids, organlca)
-	actnbbei hloudoun (dla-
aolved and auspended
aollda, organlca)
grain duat froiu aiechanlcul
collectors (pealIcldia)
3 rain duaL from
Iroct-conlact di yer
(peaLlcldea)
coal duat, fly
asli, bottom ash from
coal fired boiler
(1 not ganlca)
biological sludge from
uaaLeuatei treatment
(peaLlcldea, litiuune,
I pea
Nil j.
metals)

-------
Steam Production
Coal, oil or natural gas are the most common source of fuel
in the alcohol industry. Of course, many more environmental ob-
stacles must be addressed for the combustion of coal than of the
other two sources. Nonetheless, air emissions from the combus-
tion of any of these fuels can contain criteria pollutants. . Sot-
id wastes could include collected coal dust, fly ash, and bottom
ash from coal-fired furnaces. Sluicing systems and boiler blow-
down are two major sources of liquid effluents. These streams
may be high in total dissolved solids and trace elements. Fur-
ther, priority pollutants could appear in the sluice system.
Finally, if a recirculating cooling water system is operating at
the plant, another effluent will arise from blowdown of this
system.
Environmental Control System
Environmental control systems potentially include:
•	Wastewater treatment system;
•	Wastewater pretreatment system for pretreating plant ef-
fluents prior to off-site treatment at a municipal or
publicly owned treatment facility;
•	Wet scrubbers for flue gas cleaning;
•	Mechanical collectors;
•	On-site solid waste disposal (landfill or landfarm);
•	Fermentation vent collection system, and
•	Tank farm control equipment.
If present, a wastewater treatment system handling the plant
effluents on-site is the major control module requiring environ-
mental sampling. In keeping with the previously stated objec-
tives, characterization of plant scrubbers and mechanical collec-
tors should also be conducted. Aqueous scrubber blowdown streams
will be contaminated with organic vapors, NH3, H2S, SO2,
etc. The wastewater treatment system could produce odors and
volatile organics as air emissions. Outfall to the receiving
body constitutes the principal liquid effluent, and the solid
waste is commonly comprised of excess activated sludge. If this
sludge undergoes land disposal, leaching characteristics become
important. Aqueous scrubber blowdown streams or slurries from
mechanical collectors will be contaminated with dissolved and
suspended solids, organic vapors, NH3, H2S, SO2, and other
pollutants .
86

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SAMPLING PROCEDURES
The careful selection and execution of sampling procedures
is the most critical step in producing reliable characterization
data. Samples must accurately represent composition of the
stream samples and must be compatible with the analytical tech-
niques applied. Factors which must be considered in order Jzo
maintain sample integrity and provide " a representative scrapie
include:
•	Spatial and temporal variations in stream composition;
•	Changes in sample composition following removal from a
stream;
•	Limitations of the analytical techniques; and
•	Requirements for accuracy.
Spatial variations in composition-can-be averaged by compos-
iting aliquots collected over the cross section of a flowing
stream or throughout the volume of a static storage vessel or
pile. However, it is best to avoid these variations by selecting
a sampling location where the material is well mixed.
Temporal variations can occur for a variety of reasons,
ranging from stratification in the material source stream to pro-
cess operation fluctuations. They can be averaged by compositing
aliquots collected over a period covering all process cycles or
characterized in detail by analysis of each aliquot.
Preserving the sample integrity throughout the collection,
transport, and analysis sequence is of utmost importance. For
instance, many alcohol plant effluents contain highly biodegrad-
able compounds whose concentration is to be measured. Unless
stored at reduced temperatures (about 4°C) to decrease biological
activity, a determination of the biochemical oxygen demand (a
measure of the biodegradable organic concentration) will be inac-
curate.
Both manual and continuous sampling are available techniques
for the characterization of an alcohol facility. The methods and
type of test plan discussed in this report are oriented toward
the intermittent manual techniques. This focuses the sampling
program described herein on short-term compliance verification
and permit support analysis.
Gases
The major sources of emissions and the components of these
sources are presented in Table 33. In addition to identifying
87

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the chemical components of the stream, the selection, design, and
execution of sampling procedures for gas streams requires knowl-
edge of the following:
•	Stream physical conditions;
•	Reactivity of stream components relating to both sample,
•stability and~~safety" considerations ; and
•	Physical arrangement of the piping or ducting containing
the stream.
The temperature and pressure of the gases from the condenser
vents, the fermenter vents, and the mechanical collector exhausts
are near ambient conditions and warrant no special sampling pro-
cedures related to these physical parameters. Since the flow
from condenser vents is often variable in an alcohol plant, con-
tinuous monitoring devices should be used when possible. The
presence of high concentrations of water vapor in streams such as
the exhaust from the cycles on the-by-product - dryer may interfere
with collection devices. In these instances, the gases can be
passed through a drying column or osmotic membrane to remove the
moisture prior to collection. Well-documented procedures exist
for sampling flue gas species such as EPA Method 7 for N0X and
EPA Method 5 for particulates.
In regard to safety, the emission of volatile hydrocarbons
in alcohol plants dictates that only explosion-proof sampling
methods are to be employed. This means that battery-operated
pumps and samplers, grab techniques, or impingers must be used.
Also, since benzene emissions are suspended from the condenser
vents on the dehydration column and stripping column, respirators
should be worn when sampling in these areas.
The appropriate stream and piping must be examined for ac-
cessibility. If no sampling port is available, location and con-
struction of a port is required. Method 1, promulgated by the
EPA, presents criteria for selecting a gas stream sampling point.
Liquids
Many liquid effluents from an ethanol plant are relatively
high in biodegradable organics. Preservation techniques such as
chilling to inhibit biological breakdown of organics is necessary
to maintain the integrity of the samples. Also, some analytical
parameters such as metals, ammonia, chemical oxygen demand (COD),
total organic carbon (TOC), cyanides, and phenol require the- ad-
dition of acids or bases as a pre-analytical preparation. Since
settling may occur enroute to analysis for some samples high in
suspended solids, these should be filtered on-site for analysis
88

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later. Table 34 presents a summary of the preservation and prep-r
aration techniques as well as time limits for analysis associated
with liquid stream parameters.
The preferred sampling points for liquid streams are exist-
ing valves, either in-line or on a side stream. These valves
provide a ready source from the stream and should be used when,
compatible with the objectives- of the" test"-program. ~ Many alfiefhol-
plants are equipped with such valves as part of their routine
sampling program for quality control purposes. Other points of
easy access are outflow orifices where the liquid streams flow
into ponds, tanks, or other open surfaces. Open or noncontained
streams may be sampled at any point compatible with accuracy re-
quirements. The major restriction in selecting sampling points
is stream homogeneity. It may be necessary to have sampling
valves installed, to ensure a well mixed sample. Sampling should
be done just downstream from points of turbulence, such as elbows
or pump-discharge lines.
In selecting sampling methods for- liquids-, -the analytical
techniques planned must also be considered. For example, glass
containers must be used when sampling for pesticides, benzene,
phenols, base/neutrals, and purgeables since plastic containers
may provide interference during analysis. Samples may be taken
at regular intervals over the duration of the test and then
either analyzed individually or combined to provide an averaged
sample. If possible, the test duration should be long enough to
cover normal process variations.
Solids
There are two general techniques of sampling methods for
solids: grab sampling and grab-and-composite sampling. Although
the collecting methods are the same, the grab-and-composite sam-
pling is the more precise technique. Conveyed solids such as
grain or coal may be representatively sampled by compositing over
a period of time. When solids such as by-product grains, bottom
ash or collected fly ash are stored in piles or silos, stratifi-
cation can occur and obtaining a representative sample can be
difficult. Core sampling can overcome this problem in a static
storage pile or container.
ANALYTICAL METHODS
The purpose of an analytical method is to provide qualita-
tive and/or quantitative data for the analytical parameters iden-
tified in the test plan. Factors affecting the selection of
analytical techniques include:
• Compatibility with sampling procedure;
89

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TABLE 34. LIQUID SAMPLE PRESERVATION AND
PREPARATION TECHNIQUES (148)
Dissolved and
Suspended Solids
BOD
Sulfates
Iodine
COD
nh3
TOC
Pesticides
PH
Benzene
Priority Pollutants (149)
Purgeables
Base/Neutrals
Cyanides
Phenols
Metals
Preservation
Technique
Cool, 4°C
Cool,	4 C
Cool,	4°C
Cool,	4°C
Cool,	4°C ~
Cool,	4°C _
Cool,	4°C
Cool, 4 C
Cool, 4 C
Cool, 4 C
Cool, 4°C
Cool, 4°C
Cool, 4 C
Cool, 4 C
Preparation
Technique
Filter
Acidify to pH
<2 with H-SO.
2 4
Filter, acidify
to pH <2 with
h2so4
On-Site
Measurement
..Analysis
Time Limit
7 days
24 hours
7 days
24 hours
7 days
24 hours
pH >12 with
NaOH
Acidify to pH
<4 H-PO.
3 4
Filter, acidify
to pH <2 with
HNO„
6 hours
24 hours
24 hours
6 months
90

-------
•	Expected concentration ¦ level and required detection
limits;
•	Presence of interfering species;
•	Accuracy and precision requirements;
•	Requirements of the" established "quality control program:
and
•	Time, equipment and cost limitations.
Modern technology has provided the analyst with a wide range
of analytical tools, ranging from classical "wet-chemical" tech-
niques to sophisticated instrumental methods. Each analytical
parameter of interest can be identified and/or quantified by one
or more of these procedures. The selection of the optimum ap-
proach from the available alternatives requires all the skills of
a well-trained professional. Table 35 presents a summary of ana-
lytical methods which can be- used- to measure the parameters iden-
tified in the previous sections.
DATA EVALUATION PROCEDURES
The data acquired during the environmental characterization
of a fermentation alcohol facility may be critical to the suc-
cessful development of the Gasohol industry. This information
may form the basis for future environmental regulations which
might evolve as the Gasohol industry grows. Sound statistical
methods used in program design and data correlation will ensure
the acceptance of the data and provide a sound basis for
regulation, control and environmentally acceptable operation.
Statistical methods have primary uses in three areas of tne
environmental characterization:
•	Checking the reliability of collected data, establishing
confidence intervals for the data, and comparing means
(averages) for data collected at different times;
•	Evaluating the quality control performance of the sam-
pling and analysis program; and
•	Determining cause-and-effeet relationships between vari-
ables, analyzing the sources of variability in collected
data, and assessing the extent to which variables are
correlated.
Sample collection technique affects_the data characteris-
tics, each one having different ramifications on statistical
treatment of data. Four types of sample collection techniques
91

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TABLE 35. ANALYTICAL TECHNIQUES FOR AN
ENVIRONMENTAL CHARACTERIZATION
Analytical Parameter
Gases
Total hydrocarbons
Benzene
Ammonia
Particulates
Carbon Monoxide, Oxygen
Sulfur Dioxide
Nitrogen Oxides
Liquids
Total Solids
Total Dissolved Solids
Volatile Dissolved Solids
Total Suspended Solids
Volatile Suspended Solids
Biochemical Oxygen Demand
(BOD)
Chemical Oxygen Demand
(COD)
Analytical Technique
Gas chromatograph (GC) with-^
flame ionization detector (FID)
GC with FID
Colorimetric method (ness-leri-
zation) or titration with
h2so4
EPA Method 5
Orsat Analyzer
EPA Method 6
EPA Method 7
Evapogate sample to dryness
@ 105 C and record weight
Filter sample, evaporate fil-
trate to dryness @ 105 C,
record weight loss
Ignite filtrate from TDS in an
oven @ 550 C, record weight
loss
Filter sample, evaporate filter
paper residue to dryness @
105 C, record weight
Ignite dryed residue from TSS
in an oven @ 550 C, record
weight loss
Analyze for dissolved 0~ , incu-
bate (3 20 C for 5 days in the
dark, record reduction in dis-
solved O2
Oxidize sample with K2Crn07 in
a 50% ^SO^ solution (5 reflux
temperature, use Ag£S0, cata-
lyst and Hg2SO, (to remove
chloride interference), record
excess dichromate
(continued)
92

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TABLE 35. (continued)
Analytical Parameter
Liquids (continued)
Total Organic Carbon (TOC)
pH
benzene
pesticides
sulfates
ammonia
metals
iodine
Solids
benzene
pesticides
ammonia
sulfates
metals
Analytical Technique
Oxidize sample in a high-tem-
perature furnace, measure C0~
produced with infrared analyzer
On-site analysis with pH
instrument
GC analysis or GC with mass
spectroscopy (MS)
Extraction followed by GC or
GC/MS
Gravimetric or Turbidimetric
methods
Buffer with a borate solution
to pH of 9.5, use colorimetric
or titration method for analysis
Atomic absorption spectroscopy
Amperometric titration
Heat solids and withdraw over-
head vapors with a syringe,
analyze vapors with GC
Extract from solid and use GC
or GC/MS
Acidify sample, distill into
boric acid solution, use
colorimetric or titrimetric
techniques
Extract from solids with HC1,
add H«09, use barium-thorin
titration (EPA Method 5)
Oxidize organic matter with low
temperature asher, dissolve
with HC10,, use atomic
absorption
93

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are continuous monitoring., manual sampling (periodic or intermit-
tent), composite sampling, and totalizing.
Data from continuous monitors place no constraints on the
statistical data analysis. When used with an automatic data log-
ging system, they greatly increase the possible applications of
statistical analysis because:
•	More information can be handled than is possible by human
data recorders;
•	Data can instantaneously be placed in the proper formats
for statistical analysis; and
•	Preliminary on-site analysis of data is feasible in many
cases.
In the case of manual sampling, the frequency or number of
samples collected during the characterization test is important.
The limitations of each sampling and- analytical method must" be
considered in selecting both the variables to be evaluated and
the statistical methods to be used. Also, for manual sampling
and analysis methods, the test plant should ensure that the final
data logging procedures are in formats which minimize data trans-
fer and the possibility for error.
Compositing is an averaging technique in which sample ali-
quots are collected over a relatively long period of time and
either combined to obtain an average sample for analysis or re-
tained as separate entitites for analysis. In the first case, a
composite sample is collected, while in the latter, a composite
average is developed after analysis is completed. The latter
technique should be used at least initially to ensure that suffi-
cient aliquots are collected to yield a good average sample.
Totalizers are counting devices used to indicate the genera-
tion of consumption of some entity. In some cases, such as coal
totalizers in power plants, data (sample) collection is merely
the reading of a meter and the frequency is at the discretion of
the test plan designer.
Quality Control
A quality control program is intended to prevent the prop-
agation of bias through the sampling/analysis/evaluation chains
of the test progam. The statistical methods commonly used in
maintaining a quality control program are relatively simple and
should be performed in the field to ensure rapid feedback of
information when a loss of control is indicated. The most common
types of analysis are correlation tests and regression tests used
94

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for estimating data variability and the maintenance of control'
charts. The' features of correlation analysis are summarized
below:
•	Gives a quantitative assessment of the extent to which
two parameters are linearly related;
•	Requires only that data for the two parameters be col-
lected in pairs; and
•	Cannot be used by itself to study cause-and-effect rela-
tionships between variables.
In comparison, regression analysis offers the following features:
•	Provides an estimate of error in the data generation
chain;
•	Provides an estimate of the dependence of one variable on
one" or more other variables;
•	Can be used to develop a simulation model of a process or
process module;
•	Requires that only the dependent variables be influenced
by error; and
•	Is difficult to use in field tests when more than one in-
dependent variable is involved.
Quality control charts have several potential uses:
•	To determine acceptable levels of data quality;
•	To achieve the acceptable levels; and/or
•	To maintain the acceptable levels.
These charts can be used for such quality control data as: re-
plicate samples, isokinetic sampling rates, EPA sampling train
calibration factors, and "spiked" sample recovery results. For
most applications, control limits are set at three standard de-
viations for replicate results.
In regard to maintaining quality assurance during analysis,
the following procedures are recommended:
•	Duplicate testing;
•	Frequent calibration of analytical equipment with stan-
dards and spiked samples;
95

-------
•	Analyzing blanks;
•	Monitoring with quality control charts;
© Conducting daily GC/MS system performance evaluations;
and
•	Distilling standards to confirm distillation efficiencies
and reagent purity.
96

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SECTION 7
TEST PLAN
This test plan consists of a set of procedures which will
accomplish the objectives outlined below. This plan is based on
the general sampling and analytical requirements outlined in Sec-
tion 6, but has been modified for a particular alcohol plant.
OBJECTIVES AND SCOPE
The objectives of the environmental characterization of a
fermentation ethanol plant for-this test plan are:
•	A delineation of the identities and amounts of pollutants
in gaseous, liquid, and solid waste effluent streams;
•	A determination of pollutant removal performance of
existing control modules; and
•	A determination of the fate of pesticides and benzene in
the process route.
To satisfy the first objective an effluent characterization
was completed in which every effluent stream (gas, liquid, or
solid) from the plant was reviewed to determine whether it con-
tained pollutants.
To address the second objective, a control module character-
ization was conducted where the influent and effluent streams of
each pollution control device was sampled.
To complete the third objective, internal streams suspected
of containing the hazardous compounds were scheduled to be sam-
pled to determine where these substances are destroyed or emitted
from the alcohol facility.
PROCESS ANALYSES
A thorough analysis of process equipment and operating
parameters was made in this section to assure accuracy and effi-
ciency. This anlaysis consisted of the fo-llowing steps:
•	Identification of process streams to be sampled and their
important analytical, parameters;
97

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•	Selection of a process stream-analytical parameter ma-
trix;
•	Identification of the process operating parameters which
should be monitored prior to and during execution of the
test plan;
•	Selection of the sets of operating conditions for "Which-
characterizations will be made; and
•	Designation of the stream and analytical parameter combi-
nations for which data from other sources (plant records
and operating personnel) will be adequate.
Process Description
To address the first two steps, the process flow diagram for
the alcohol facility (Figure 5) was broken down into nine compo-
nents and each stream sampled was identified with a number for
future reference. A brief - description of each component is pre-
sented and the analytical parameters of interest for each stream
are summarized according to process unit (Table 36) and in a sam-
pling matrix (Tables 37 through 39).
A general description of an alcohol facility has been given
in Section 3. The particular plant sampled does differ from the
conceptual plant in several ways. One major difference in this
plant is its operation in conjunction with a protein extraction
unit which removes some of the protein, oils, and starch and pro-
vides a high-sugar content feedstock for the alcohol process.
Since this processing scheme is not an integral part of a typical
alcohol plant, it was not included in the characterization. The
alcohol plant also derives part of its feedstock from on-site dry
milling operations; this unit, which is typical of most alcohol
plants, was considered within the scope of the characterization.
In the conceptual design, the source of steam was from a
coal-fired boiler. Steam for this plant is produced from an on-
site boiler which uses natural gas 9 months of the year and No. 6
fuel oil for the remaining 3 months. At the time of sampling,
natural gas was the source of fuel for the boiler. Since no
electricity is generated on-site, the fuel requirements are de-
termined strictly by process heat needs.
Another deviation from the "typical" alcohol facility is
that the flue gases from the boiler are routed to the direct con-
tact dryer where water is removed from the by-product distiller's
dried grains (DDG). The dried gases are then sent to cyclones
for particulate removal. Thus, there are no direct boiler fur-
nace emissions from the alcohol plant.
98

-------
tlourlfruM
Piot tin E»U*ttg
Hi I
Bee*
Uell
euaraioi
Bear
Still
Sulvatii
MiyJiailiai
(bltwi
ill
utrictoi
HecclfIcr
Buizeue
Hokeup Slew*— *-
I-
St oan
Clltdtiul
Sterna
J
uuCiIfug

Criln
0)
'	luuti 10
_ S^|__L:
•— n t..,. C'„„ior 	,r
.-j	l_—_——JCoiiileiiaui l
t	__L,tolB11,	"i®
(Si) fo*"* Ikll J
"i® ®
©
tltcDllLli
Airat Iuii
and
lai IfleCi
~l 4.1111 Itllftl
{£) Traaiad
~ -et flueuc
I- —+¦ trr jue
lo fiiw
©
Bui lei
Olowtlawii
Figure 5. Alcohol plant flow diagram.

-------
TABLE 36. ALCOHOL PLANT EFFLUENT SOURCES AND EMISSIONS
?rocas3 Uaic
Gaseous Emissions
Liquid Effluents
Solid Wasces
Grain Preparation Hone
Mone
Cooking and Cool-
in?
Conversion a Tin
Fermentation
Condenser Venc
(hydrocarbons)
CO, Scream
(hydrocarbons)
Gram Dust, Chaff
and Dirt Recycled
Flash Cooler Con- None
densata (dissolved
and suspended solids,
organics)
"eimentar x'asn Vater Mone
(dissolved and sus-
pended solias,
organics, alkali,
iodine)
Discxilaclon
Condenser Vent
(Hydrocarbons)
Mone
None
Purification
Rectification
Dehydration
Condenser Venc
(hydrocarbons)
Condenser Vent
(hydrocarbons)
Condenser 7ents and
Vent on Separator
(Senzene and other
hydrocarbons)
Solvent Extractor Hone
and Fusel Oil
Column Bottoms
(dissolved and sus-
pended solids,
organics)
Ssctlfier Column	Mone
3oc corns (a is so 1 ved
and suspended solids,
organics)
Stripping Column	Mone
Bottoms (Benzene,
Ethanol, Fusel Oils,
and other organics)
3y—Produce
Processing
Wastewater
Treataanc
Evaporator
Condenser Venc
(hydrocarbons)
Cyclone Off-Gases
sov SOj, CO,
particulates)
Fugitive emissions
organics)
Evaporacor and
Barometric Conden-
sate (dissolved
and suspenaed
solids, organics)
Treatad if fluent
from Wastewater
Treatment
Grain Dust col-
lected by cyclone
(recycle to dryer)
Screened solia
and olologlcal
sludge (recycled
to dryer)
100

-------
TABLE 37. SAMPLING/ANALYTICAL MATRIX - SOLIDS
Animal Biological
Grain DDG Feed	Sludge
Analytical Stream
Parameters Number 1 22 26	32
Benzene -X X	OC
Pesticides XXX	X
Ammonia XX	X
101

-------
TABLE 38. SAMPLING/ANALYTICAL MATRIX - GASES
Cyclone
Grain	Condenser
Preparation	Vent
Flash
Cooler
Inlet Outlet
Analytical Stream
Parameters Number 2	3
8
Condenser Vent
Ferraenter Beer Solvent
Vent	Still Extractor Rectifier
10
12
14
Total Hydrocarbons	X	X	X	X	X
Ammonia	X
(Particulates	X	X
(continued)

-------
TABLE 38. (continued)
Analytical Stream
Parameters Number
Condenser Vents
Fusel Oil
Column
16
Dehydration
Column
18
Separator
Vent
19
Condenser
Vent
Stripping
Column
20
Cyclone
Dryer Dryer
Inlet Outlet
23
24
Condenser
Vent
Evaporator
28
Total Hydrocarbons
Benzene
Ammonia
Particulates
Carbon Monoxide
Sulfur Dioxide
Nitrogen Oxides
X
X
X
X
X
X
X
X
X,
X
X

-------
TABLE 39. SAMPLING/ANALYTICAL MATRIX - LIQUIDS
City
Makeup
Water
Milled
Grain
(Cooker
Feed)
Flash	Solvent	Fusel Oil
Cooler Fermenter Extractor Rectifier Column
Condensate Outlet Bottoms Bottoms Bottoms
Analytical Stream
Parameters Number
11
13
15
Dehydration
Column
Bottoms
17
Total Solids	X
Total Dissolved
Solids	X
Volatile Dissolved
Solids	X
Total Suspended
Solids	X
Volatile Suspended
Solids	X
BOD	X
COD
TOC	X
pH	X
Benzene	X
Ammonia	X
Pesticides
Sulfates	X
Copper	X
Iron	X
Iodine	X
X
X
X
X
X
X
X
X
X
X
X
X
(continued)

-------
TABLE 39. (continued)
o
u*
Stripping	Cooling VersM-nteY
Column Barometric Evaporator Tower	Uau\\	Well
bottona Condensate Condeutiute Blowdcwu Water Water
Analytical Stream
Paraaeiera Number
21
Total Solids
Total 1)1 a solved
So II da
Volatile Diosolved
Solldu
Total Suspended
Solldu
Volatile Suspended
Solldu
ttOD
COD
TOC
pu
Benzene
Anuiortlu
PehtlLldea
SuLfatuu
Copper
Iron
lodl IIU
25
27
29
10
31
uu
Creatinent
I Ik f Ul£llt
33
UVI
Treatment Boiler
b'fflueiit Ulouduwn
J4
35

-------
In addition to a beer still and a rectifier, this plant has
a solvent extractor and a fusel oil column to aid in separating
higher alcohols and other impurities from the ethanol product.
These units would not be necessary in an alcohol plant designed
solely for fuel production.
Finally, in the alcohol plant sampled., all solid was_t-e-r
grain dust, wastewater treatment sludge, and screened solids are"
recycled to the dryer for DDG production. Therefore, no solid
waste requiring disposal is generated from this alcohol plant.
Analytical Parameter Selection
Grain Preparation--
The first unit in the alcohol product route is grain prepar-
ation. As Figure 6 shows, whole grain is pulverized using hammer
mills. The chaff and dirt which is shaken loose and grain dust
which is collected by cyclones is sent to the dryer for DDG
production. The milled grain is then slurried with water and
sent to the cooker.
Analytical parameters which were scheduled for evaluation
included particulate concentration in the influent and effluent
streams for the cyclones and pesticide levels in the whole grain
and in the feed stream to the cooker. Also, the makeup water to
grain preparation was tested for total solids (TS), total dis-
solved solids (TDS), volatile dissolved solids (VDS), total sus-
pended solids (TSS), volatile suspended solids (VSS), BOD, TOC,
pH, benzene, ammonia, pesticides, sulfates, copper, iron, and
iodine to establish baseline data for these parameters.
Cooking and Cooling--
In the next step, flour from the protein extraction unit and
the milled whole grain is gelatinized and solubilized in the
cooker. The cooked grain then passes to the flash cooling equip-
ment which consists of a series of vacuum chambers where heat is
removed by evaporating some of the water from the slurried grain.
(Refer to Figure 7).
Although the overhead condensate was expected to have a low
BOD and contain a relatively small amount of solids, this stream
was tested for these parameters, as well as for pH. Also, the
flash cooker condensate was monitored for the presence of pesti-
cides. Finally, the vent on the flash cooler condenser was
measured for total hydrocarbons.
Conversion and Fermentation--
Figure 8 presents a schematic diagram of conversion and
fermentation. Enzyme is added to the solubilized starch in the
converter tank where the starch is broken down into component
sugar molecules. The yeast then metabolizes the sugar into
106

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Atmosphere

©
Cyclones



©
Collected Dust
to Dryer
Grain Dust
Grain Preparation
(Hammer Mills and
shakers)
©
©
Makeup
Water
Milled Grain
to
Cooker
Chaff & Impurities
to Dryer
Figure 6. Grain preparation.
107

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Flour from
Protein Extraction'
Milled Grain
Thin Liquids from
Centrifuge
Cooked Grain
to
Flash Cooler
Condenser Vent
to Atmosphere
Cooked Grain
©


Flash

Cooler



Condensate to
Cooling Tower
Mash to
Converter
Figure 7. Cooking and cooling.
108

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Starch from ^


Flash Cooler
Converter

Enzyme »
Tank

To Fermenter
Converted Starch
Yeast
C0~ Stream
to
Recovery Units

Fermented Mash
to Beer Well
Wash Water
to WW Treatment
Mash from
Fermenters

Beer
Well





To Beer Still
Figure 8. Conversion and Fermentation.
109

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ethanol and carbon dioxide in the fermenter. The fermented mash
is routed to a holding tank (called the beer well) prior to
distillation.
The carbon dioxide stream contains small amounts of ethanol
and water vapor along with traces of other organic compounds such
as acetaldehyde and furfural, which are by-products of fermenta-
tion. - This stream was scheduled to be "sampled for ammonia-'--and-
total hydrocarbon content. Since the fermenters are washed after
each batch with a 25 ppm iodine solution, the wash water was
tested for this element in addition to TS, TDS, TSS, BOD, TOC,
pH, ammonia, and pesticides. To help trace the fate of pesti-
cides , the fermenter output stream to the beer well was also
screened for pesticides.
Distillation--
In the beer still, the fermented mash is separated into an
alcohol-rich overhead stream and an aqueous bottoms streams
containing a high level of solids. These solids are comprised
largely of yeast cells, protein, and fibers.
As Figure 9 indicates, the only effluent stream that is not
routed to another process unit is the vent on the overhead con-
denser. This stream was tested for total hydrocarbons.
Purification--
As Figure 10 illustrates, purification involves the addition
of water to aid in the separation of higher alcohols (fusel oils)1
and aldehydes-from ethanol.
The aqueous bottoms from the solvent extractor and fusel oil
column which are sent to wastewater treatment were tested for TS,
TDS, TSS, BOD, TOC, and pH. Also, the vents on the overhead con-
densers from these columns release volatile organics. These vent
streams were analyzed for total hydrocarbon content. The fusel
oils extracted during purification are sold as by-products and
were riot examined.
Rectification--
In the rectifier, the aqueous alcohol stream from the sol-
vent extractor is concentrated to 95 to 96 percent ethanol.
Residual impurities such as fusel oils are also removed in this
column. (See Figure 11).
The vent on the overhead condenser was analyzed for total
hydrocarbons and the rectifier bottoms was analyzed for TS, TDS,
TSS, BOD, TOC, pH, and pesticides.
110

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Condenser Vent
to Atmosphere
Feed-from
Beer Well
Beer Still
Ethanol/Water
-*¦ to
Solvent Extractor
Bottom Stillage
to Centrifuge
Figure 9. Distillation.
Ill

-------
Condenser Vent
to Atmosphere
Feed from
Beer Still
Fusel Oils
To Rectifier
Recycle from
Fusel Oil
Column
From
Rectifier
Reflux to
Fusel Oil
Column
Extractor
Solvent
To Cooling Tower
Condenser Vent
to Atmosphere
Feed from
Rectifier"
Fusel Oil
Column
¦Fusel Oils
To Solvent
Extractor
Column Bottoms
to Cooling Tower
Figure 10. Purification.
112

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Condenser Vent
to Atmosphere

©



Ethanol to
Feed From r
Rectifier
~Dehydration Column
Solvent Extractor

To Fusel Oil


* Column

©

Bottoms to Solvent
Extractor Bottoms Tank
Figure 11. Rectification.
113

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Dehydration--
In the dehydration sequence illustrated in Figure 12,'
benzene is used to form a ternary azeotrope with the
ethanol/water feed to the dehydration column. Addition of the
proper amount of benzene causes nearly all of the water and
benzene to leave the top of the column while ethanol is withdrawn
from the bottom of the column. _A chilled separator and_-a
stripping column are used to remove water from the dehydration-
column overhead stream (via the stripping column bottoms) and
recycle benzene back to the dehydration column.
Ethanol withdrawn as bottoms from the dehydration column was
analyzed for TS, TDS, TSS, and benzene. The water stream from
the stripping column may also contain benzene and other organic
compounds. In addition to benzene, this stream was analyzed for
TS, TDS, BOD, TOC, and pH. Air emissions from the vents on the
overhead condensers and the separator were analyzed for benzene
and total hydrocarbon content.
By-Product Processing--
As Figure 13 shows, the water in the bottoms stillage from
the beer still is removed using centrifuges, multi-effect evap-
orators, and a direct-contact dryer.
Three streams associated with the evaporators were examined
for pollutants, including the overhead condensate, barometric
condensate from the vacuum ejectors, and air emissions from con-
denser vents. The overhead and barometric condensate were tested
for TS, TDS, VDS, TSS, VSS, BOD, TOC, and pH. The vent streams
on the condensers for the evaporators were analyzed for total hy-
drocarbons .
Particulate emissions are the major concern for the direct-
contact dryer. Particulate levels will be checked in the inlet
stream as well as in the effluent stream from the cyclone to de-
termine the pollutant removal performance of this control module.
Because boiler flue gases are used in drying, SO2, CO, and
N0X levels were monitored in the exhaust from the dryer cy-
clones .
Wastewater Treatment-
Cooling tower blowdown (which is comprised of condensate
from the evaporators, the flash cooler, and the barometric
condensers as well as the bottoms from the solvent extractor, the
rectifier, and the stripping columns), and equipment wash water
are routed to a sludge pit where they are diluted with well water
as Figure 14 reveals. This wastewater, along witn thin liquids
from the centrifuged wastewater biosludge, is passed through
screens to remove large particles and fibers and then routed to
extended aeration ponds and clarifiers for biological treatment.
114

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Condenser Vent
to Atmosphere
Feed from
Rectifier
Reflux from
Separator

@


Dehydration
Column


	~

©
Overhead Condensate
Ethanol to Storage
Vent to
Atmosphere
Feed from
Dehydration
and Stripping
Columns
Top Phase to
Dehydration Column
Bottom Phase to
Stripping Column
Condenser Vent
to Atmosphere
11
Reflux from
Separator
Column
Overhead Condenser
to Separator
Bottoms to
Wastewater Treatment
Figure 12. Dehydration.
115

-------
Bottom Stlllage
froo	>
Beer Still
Cake froo
WW Treatment —*¦
Centrifuge
()i»nt"r i ftigp
CT>
Feed from Centrifuges
Evaporator, Screens, &
Particulate Control
Recycled U1)G
Figure 13
Condensate Co
Cooling Tower
Condenser Vent
to Atmosphere
~~1 Vacuum Line I
rliln Liquids
	to
Evaporator &
Cooker
Fe*«l from
Centrlfuge
Cake to
Dryer
l)DG Recycled/
Animal Feed
Boiler Flue
Cyclone
Dryer
Evaporotor
Condensate to
-Cooling lower
Bottom** lo Drye
Animal Feed
Boiler Flue
Cases
By-product processing.

-------
Cooling Tower

Slowdown (?)

Eauiomenc Wasn
Sludge
Wacer GO)
Pic
WaU (7\

Wacer ^



To WW Treacaenc
Boiler
31owdovo
vJW : rom 	
Sludge ?ic
Thin Liquids
from w"W-
Treacmenc
Cancnfuge
©
extended
Aeracion
and
Clarifiers
.Trsaced Efrluenc
~:o River
_ Sludge co
Cancrifuge
WW Treacaenc
Sludga
HW Treacaenc
Thin Liquids
co
@ Treacaenc
¦ Caica co Dryer
Figure 14. Wastewater treatment.
117

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Un-treated blowdown from the boiler is added to the treated efftcr*
ent prior to discharge into the river. All solid waste from this
system is sent to the dryer for inclusion in the DDG product.
The cooling tower blowdown stream was tested for TS, TDS,
VDS, TSS, VSS, BOD, COD, TOC, pH, benzene, pesticides, sulfates,
copper., iron, and iodine due._to the, quantity and types of streams-
which make up the feed to the cooling towers. The blowdown
stream was also screened for priority pollutants.
The well water was analyzed for TS, TDS, VDS, TSS, VSS, BOD,
TOC, pH, benzene, ammonia, sulfates, copper, iron, and iodine.
To determine the pollutant control performance of the waste-
water treatment system, both the influent and effluent streams
were tested for TS, TDS, VDS, TSS, VSS, BOD, COD, TOC, pH, ben-
zene, ammonia, pesticides, sulfates, copper, iron, and iodine.
Both influent and effluent from wastewater treatment were screen-
ed for priority pollutants according to EPA protocol. Also,
boiler blowdown which is added to the treated effluent stream
from the clarifier was tested for TS, TDS, TSS, copper, and iron.
Finally, the cake from the centrifuged biosludge stream
which is recycled to the dryer was analyzed for benzene, pesti-
cides, and ammonia.
Sampling/Analytical Matrix
A sampling/analytical matrix is a convenient means of dis-
playing the set of sampled streams and analytical parameters.
Such a matrix clearly indicates the analytical parameters to be
measured in each sampled stream. The sampling/analytical ma-
trices for solid, gaseous, and liquid streams for the alcohol
plants sampled are presented in Tables 37, 38, and 39, respec-
tively.
Operating Parameters
A major purpose of the process analysis is to identify pro-
cess variables which have significant effects on stream analyti-
cal parameters. Process variables which are important in an
alcohol plant include: feedstock composition, production rate,
control module operating parameters, and other basic operating
parameters (e.g., temperatures, flow rates, pressures).
Once the principal determinants of stream analytical param-
eters have been established, the sets of operating conditions to
be characterized can be selected. If cause-and-effect phenomena
are to be statistically analyzed, the te-sted sets of operating
conditions must be based on a valid experimental design.
118

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In this alcohol plant characterization, sampling will be
conducted only at steady state or "normal" operating conditions -
However, it is believed that only a few analytical parameters
would be significantly affected by the changed conditions.
Existing Process Data-
Due to time and budget restraints,- data on several streams
may be taken from plant-records as * collected" by operating plant
personnel or regional EPA personnel. No data will be used un-
less it has been collected in an acceptable manner and certified
by regional EPA personnel.
Sampling Procedures
Sampling procedures may be grouped into two basic catego-
ries: manual methods and continuous sampling. The manual
methods are generally more flexible, more easily executed, and
more labor intensive. Continuous automated techniques are more
complicated and more capital intensive. Section 6.3, Sampling
Procedures,- presents -a- detailed discussion concerning the
selection of sampling techniques. This section, along with the
process analysis and site visit, was used to determine:
•	Approximate sampling location for each sampled stream;
•	Sample collection procedures for each location and analy-
tical parameter; and
•	Handling and preservation techniques for each sample.
Some important considerations in finalizing the specifica-
tions include:
•	Possible last-minute process or equipment modification;
•	The steps for ensuring needed cooperation between plant
operator, sampler, sample handler, and analyst in a field
test situation;
•	Revisions to approved regulatory agency test methods or
agency approval of more convenient test methods; and
•	Health and safety ramifications of the proposed port lo-
cations and sampling methods (e.g., toxic or explosive
gases, high internal pressures and/or temperatures, ele-
vated or exposed positions).
The following sections discuss the techniques chosen for the
collection of material from the solid, liquid, and gas streams
which were identified in the previous section. Also presented in
119

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this section is the tentative test schedule for the sampling ef-
fort .
Solids--
There are two general techniques for sampling methods for
solids: grab sampling and grab-and-composite sampling. Althougn
the sample collecting methods are identical, grab-and-composite
sampling is the more precise technique. ' In- this method, the grab,
samples are collected periodically over the duration of the test
and then composited to form a single sample. The grab-and-compos-
ite technique will be used to collect all solid samples in the"
characterization.
Three of the solid streams (whole grain, grain dust, and
DDG) are sufficiently dry and free-flowing to be collected using
the shovel technique. Since these streams are believed to be
relatively homogeneous, there should be no problems in obtaining
a representative sample. Samples will be collected in clean,
1-liter containers every 2 hours for an 8-hour period and then
composited.
The quantity of material collected in this sampling method
will yield much larger quantities than are needed for analysis.
The technique' that will be used to reduce the sample size with-
out affecting the distribution of componential samples is called
the coning and quartering method. This method consists of shap-
ing the sample into a conical pile which is then sharply divided
into quarters. Two opposite portions are combined and the com-
posite is then further reduced by again coning and quartering.
This is repeated until a sample of the desired 1-liter size is
obtained.
The remaining two streams (animal feed and wastewater treat-
ment sludge) have a high concentration of water and cannot be
collected and handled as tne above streams. Instead, samples
from these streams can be collected in 200-ml portions every 2
hours for 8 hours and then composited to obtain the desired
1-liter sample.
Although no preservation techniques are necessary for the
solid samples, all will require preliminary treatment or prep-
aration prior to analysis. This includes:
•	Pulverizing the whole grain;
•	Vaporatization of ethanol, fusel oils, and benzene;
•	Solvent extraction for pesticides;
120

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•	Acidification and distillation of ammonia; and
•	Acid extraction for sulfates.
Liquids--
All liquid streams which will be sampled are single phase,
homogeneous streams. Furthermore, none of the streams will be
sampled at* high "temperatures"" or"' pressures . These conditions
greatly simplify the sampling techniques as well as reduce health
and safety concerns.
The sampling points for most of the liquid streams are ex-
isting in-line valves. These valves provide a ready source from
the stream and are currently used by the plant personnel for sam-
pling. The valves pertaining to liquid streams which contain
ethanol are sealed by the Bureau of Alcohol, Tobacco, and Fire-
arms personnel. Permission to break these seals and their sur-
veillance will be obtained prior to sampling.
- Other sampling points which will be used are outflow ori-
fices where liquid streams flow into ponds, tanks, or other open
surfaces. Liquid streams to be sampled from these plants include
the influent and effluent streams from wastewater treatment,
boiler blowdown, and fermenter wash water.
Many of the analytical parameters which will be monitored in
the liquid streams have special preservation or preparation re-
quirements. These requirements are presented in Table 40 along
with the time limits in which analysis must be conducted to as-
sure accurate test results.
Each liquid sample submitted for analysis will be the com-
posite of five 200-ml samples taken every 2 hours over an 8-hour
period. The actual test schedule is presented later in this sec-
tion .
Gases--
All gas stream sampling will be conducted at atmospheric
conditions and at moderate temperatures (20-150°C). There is one
restriction that limits equipment choice: all sampling methods
must be explosion proof. To meet this restriction, battery-oper-
ated hand pumps and samplers and grab sample techniques will be
used. Also, since the gas flow on condenser vents is expected to
be variable, the vent streams will be monitored continuously for
1-hour periods.
Most of the gas samples will require pretreatment, which
consists of absorption in liquids or on solids. The sampling
methods to be used for each parameters are presented below in
more detail.
121

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Total hydrocarbons--To sample the vents and cyclone outlet
stream on the dryer for total hydrocarbons, one end of a tube
will be inserted into the vent lines or dryer exhaust and the
other end of the tube will be connected to an organic vapor ana-
lyzer. This instrument, which has a direct read-out, will be
used for continuous monitoring.
Benzene--The collection "method for benzene will consist of
extending one end of a tube into the vent or cyclone exhaust and
connecting the other end to a personal sampler (a hand-held, bat-
tery-operated sampler). Two in-line glass tubes containing gran-
ulated charcoal (capacity is 6 liters per set of tubes) will be
used in series to absorb the benzene. The benzene is eluted from
the charcoal using carbon disulfide.
Ammonia--The samples for ammonia analysis will be collected
using a series of two Smith-Greenburg impmgers containing a 5
percent solution of sulfuric acid.
Particulates--Particulate matter"will be withdrawn isokinet-
ically from the cyclone exhaust streams and collected on a heated
glass fiber filter in accordance with EPA Method 5.
Carbon monoxide--For the collection of CO, a tube will be
inserted in the cyclone outlet stream and connected to an Orsat
analyzer. A hand pump will be used to convey the dryer off gases
through the tube to the analyzer for on-site analysis.
Sulfur dioxide--The sample for sulfur dioxide will be col-
lected using a series of two Smith-Greenburg impingers containing
a 3 percent hydrogen peroxide solution. (EPA Method 6)
Nitrogen oxide—A grab sample will be collected for nitrogen
oxide analysis using an evacuated flask containing a dilute sul-
furic acid/hydrogen peroxide-absorbing solution. This technique
is in accordance with EPA Method 7.
TEST SCHEDULE
A sampling schedule is necessary to ensure that all neces-
sary samples will be collected during the available time period
without the use of excessive manpower. At this time, four test
team members are scheduled for 3 days to complete the test plan
requirements. The tentative schedule devotes the first day to
setting up the equipment and collecting one full set of liquid
samples. Duplicate samples for selected liquid streams as well
as multiple samples of gas and solid streams will be collected
the following 2 days.
122

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_ Before the test schedule will be finalized, another survey
of all sample locations will be made prior to the arrival of the
test team to help avoid any problems which might arise. Other
considerations which will affect the final sampling schedule are:
•	The expected plant operating schedule;
•	Preparation (set-up) time requirements for sampling and
any required on-site sample recovery and analysis; and
•	Personnel and equipment availability.
Sampling frequency and timing involve decisions concerning
how often to sample and when to sample, respectively. Sampling
frequency constraints include the sampling technique itself,
plant operational variations, quality control requirements, and
data evaluation needs.
All solid, liquid, and gas streams (except for the gas
streams from the condenser- vents) will be sampled every 2 hours
over an 8-hour period and composited. The condenser vent streams
have variable gas flows and will be monitored continuously over
1-hour periods which should be sufficiently long to average out
normal process variations.
The stipulations of the quality control program and of data
evaluation will be incorporated into the sampling frequency.
Multiple samples will be taken from selected streams on consecu-
tive days in order to make an estimate of the analytical and pro-
cess variability of the data.
The general timing for samples is established largely by the
plant operating schedule. The most important factor in final
timing of the sample collection is that for any sampling, the
plant should be given sufficient time to stabilize at the pre-
scribed conditions (i.e., steady state).
Revisions in test plan content or scheduling may result due
to:
•	Changes to the plant operating schedule as a result of
equipment failures or changing objectives;
•	Identification of problems in sampling and analytical
methods;
•	Feedback of data from the quality control and data evalu-
ation programs which indicate a problem with quality con-
trol in a sample-analysis-evaluation chain; or
123

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•	Revisions of program scope arising from preliminary char^
acterization results.
Analytical Techniques
The selection of at least tentative analytical procedures is
required prior to sample collection to ensure the continuity_of
an integrated sampling/preservation/analytical scheme. The con-
siderations used in selecting the particular analytical technique
for the test effort were:
•	Expected concentration level and required detection
limits;
•	Presence of interfering species;
•	Accuracy and precision requirements;
•	Requirements of the quality control program; and
•	Time, equipment, and cost limitations.
In the following paragraphs, a brief account of the analyti-
cal methods chosen and preliminary treatments or preparations
required for the test effort is presented. The methods and pre-
treatments for the parameters are organized into sections corre-
sponding with solid, liquid, and gas streams.
Solids--
Benzene--The solid sample is heated in a glass container
which is rotated in a hot oil bath. Then the overhead vapors are
withdrawn using a syringe and injected into a gas chromatograph
for analysis. The detection limit for benzene using this tech-
nique is about 1 ppm.
Pesticides--The method for pesticide analysis involves ex-
tracting the pollutant from the solid sample and submitting it
for gas chromatograph analysis using an EPA-documented technique.
The detection limit for pesticides is 10 ppb or less using this
method.
Ammonia--The concentration of ammonia in solid samples is
determined By acidifying the sample, distilling the ammonia into
a boric acid solution, then using colormetric or titrimetric
techniques. The detection limit for this methid is about 1 ppm.
Sulfates--The sulfates are extracted from the solids using
an acidic medium (HC1). Next, hydrogen peroxide is added to this
extract to convert all the oxidized sulfur species to sulfate.
124

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Then, an analysis for sulfates is performed by the barium-thorium
titration method as specified in EPA Method 6. The detection
limit for sulfates in the liquid medium is about 5 ppm.
Liquids-
Total solids--To analyze for total solids content, an ali-
quot of the sample is evaporated to dryness at 105°C and weighed
on a Mettler balance. An alternative to analysis for total
solids is to report it as the sum of total dissolved solids and
total suspended solids.
Total dissolved solids--To determine the amount of dissolved
solids-] an aliquot of the sample is filtered and the filtrate is
then evaporated to dryness at 105°C and" weighed.
Volatile dissolved solids—The residue that is obtained from
drying the filtrate of the total dissolved solids sample is ig-
nited at 550°C in an oven. The weight loss is then reported as
volatile dissolved solids.
Total suspended solids--An aliquot of the sample is filtered
and the residue collected on the filter is dried to a constant
weight at 105°C.
Volatile suspended solids--The residue collected on the fil-
ter and dried to a constant weight for total suspended solids de-
termination is ignited at 550°C in an oven. A glass fiber filter
without an organic binder is used and the weight loss is reported
as volatile suspended solids.
Biochemical oxygen demand (BOD)—An aliquot of the sample is
analyzed for dissolved oxygen (membrane electrode method) and
then incubated at 20°C for 5 days in the dark. The sample is
then analyzed again for dissolved oxygen. The reduction in the
dissolved oxygen concentration is a measure of the BOD.
Chemical oxygen demand (COD)--The organic and oxidizable in-
organic matter in the sample are oxidized by potassium dichromate
in a 50 percent sulfuric acid solution at reflux temperatures.
Silver sulfate is used as a catalyst and mercuric sulfate is used
to remove chloride interference. The excess dichromate is ana-
lyzed to provide a measure of the COD.
Total organic carbon (TOC)--This test is performed by in-
jecting a known quantity of sample into a high-temperature fur-
nace. The organic carbon is oxidized to carbon dioxide in the
presence of a catalyst. The carbon dioxide that is produced is
quantitatively measured by means of an infrared analyzer. Acidi-
fication and aeration of the sample prior, to analysis eliminates
errors due to the presence of inorganic carbon.
125

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£H--The pH of the liquid samples is measured using a labora-
tory pH instrument having a glass electrode in combination with a
reference potential electrode.
Benzene--The analysis for benzene is conducted using stan-
dard gas chromatographic techniques. The detection limit for
benzene using this method is approximately 100 ppb.
Pesticides--The pesticides are extracted from the liquid
streams and submitted for GC analysis according to documented EPA
methods; the detection limit is 10 ppb.
Sulfates--Analysis for sulfates is performed using the Grav-
imetric Method. Sulfate is precipitated as barium sulfate m a
hydrochloric acid medium by tne addition of barium chloride. A
precipitate is formed (BaS04> and filtered, washed with hot
water, ignited, and weighed. The detection limit is estimated to
be 10 ppm.
Ammoma--An aliquot of the sample is buffered with a borate
solution to a pH of 9.5 in order to decrease the hydrolysis of
cyanites and organic nitrogen compounds. Next, the sample is
distilled into a solution of boric acid. The ammonia in the dis-
tillate is determined colorimetrically by nesslerization or
titrimetrically with standard sulfuric acid with the use of a
mixed indicator. (The choice is dependent on the ammonia con-
centration) .
Copper and iron—Analysis for these elements is performed
using atomic absorption spectroscopy. The detection limits for
copper and iron are 0.05 ppm.
Iodine--An amperometric titration method is used for the
analysis ol iodine in liquid waste streams. The detection limit
for iodine using this technique is 7 ppm.
Gases--
Total hydrocarbons--An organic vapor analyzer (OVA) which
consists oi a portable GC with a flame ionization detector will
be used to measure total hydrocarbon content of the vapor streams
from the condenser vents as well as the vents on the separator
and fermenter. The instrument will be calibrated using different
concentrations of a hydrocarbon species (Methane). Total hydro-
carbon content will be ready as ppm methane.
Benzene--As mentioned in Section 7.3, this organic compound
is collected on granulated charcoal contained in a series of
glass tubes. The sample will be eluted from- the charcoal using
carbon disulfide. The carbon disulfide effluent was analyzed for
benzene using a gas chromatograph with a flame ionization detec-
tor. The detection limit for this method is estimated at 1 ppm.
126

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	 Nitrogen oxide--The grab sample collected for nitrogen oxide
analysis is subjected to a colorimetric method using the phenol-
disulfonic acid (PDS) procedure. This technique is in accordance
with.EPA Method 7 and can be used to determine all nitrogen ox-
ides except nitrous oxide. The detectability limit for this
method is 2 to 400 mg per m3 .
DATA EVALUATION
This section presents the general approach for the analysis
of data which should be employed to verify the reliability of
collected data, to evaluate the quality control performance of
the sampling and analysis program, and to analyze the sources of
variability in collected data.
Sample collection techniques affect the data characteris-
tics, which, in turn, affect the statistical treatment of the
data. The collection techniques applied to this sampling program
will include continuous monitoring, manual sampling (periodic or
intermittent) and composite sampling. A description of these
techniques and their effects on statistical treatment of data is
presented in Section 6.5. Estimates of data variability to be
included in the test effort will include standard deviation and
confidence intervals.
Quality Control
To provide assurance that the collection of samples will be
both accurate and precise, the quality control program conducted
on-site included the following elements:
•	Calibration of both sampling and on-site analytical
equipment to establish accuracy;
•	Replicate sampling to establish the limits on precision;
•	The use of alternative (replicate) sampling analysis
methods and correlation analysis of the results as judged
necessary by the sampling team leader to confirm accu-
racy; and
•	The establishment of a chain of responsibility for data
generation, which extends from sample collection to sam-
ple recovery to sample analysis. (This will be done by
means of a strict record-keeping system which includes a
master log for tracking samples).
The quality control program which was implemented to ensure
accurate and precise analytical results consisted of:
127

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Calibration of analytical equipment with standards and
spiked samples (for all analyses except solids determina-
tion) ;
Duplicate testing (all analyses);
GC/MS system performance evaluation (for priority pollu-
tant analyses except metals);
Analysis of blanks (organics analyzed by purge and trap,
technique and metals); and
Distillation of standards to confirm distillation effi-
ciency and reagent purity (cyanides and phenols).
128

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SECTION 8
SAMPLING AND ANALYSIS OF AN ALCOHOL FACILITY
A brief account of the sampling trip is presented in this
section. Highlighted are the deviations which occurred from the
test plan described in Section 7. Included are any omissions or
additions in the sampling effort as well as changes in sampling
procedures or analytical methods. These deviations are discussed
in terms of the solid, liquid, and gas streams sampled.
TEST PLAN DEVIATIONS
Solid Streams
No problems were encountered concerning the collection,
preparation, or analysis of the solid stream samples. All sam-
ples were collected during the second and third days of the sam-
pling effort.
Liquid Streams
The first day of the sampling effort for liquid streams was
devoted to preparations such as labeling sampling containers, ad-
ministering acid or base preservation chemicals, weighing filter
papers, and devising a daily sampling schedule. To formulate
this schedule, the location and accessibility of all the streams
were reviewed which resulted in the addition of several streams
to the sampling effort. These streams included:
•	The well water makeup stream to the sludge pit since it
is a major portion of the input to the wastewater treat-
ment system; and
•	The feed stream to the cooker for pesticide analysis in
order to better follow the fate of pesticides in the al-
cohol process.
Also, it was believed impossible to sample the fusel oil column
bottoms and the solvent extractor bottoms because they are mixed
shortly after leaving the columns. Closer inspection of this
system revealed the existence of sampling ports upstream of the
point where the column bottoms are combined. Therefore, each of
these streams was sampled separately.
129

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During Che course of the sampling effort, two modifications
were made to the sampling techniques:
•	Although the .alcohol plant was known to have three cool-
ing "towers, it was assumed the water quality from each
was similar and that one would be randomly chosen for
sampling. However, plant personnel advised that the
water from- one -tower in particular was considerably dif-
ferent from the other two towers. Since two additional
liquid streams had already been added to the sampling ef-
fort, time did not permit for each cooling tower to be
sampled separately. Therefore, blowdown from all three
cooling towers was composited to obtain a representative
sample of the total cooling tower blowdown.
•	Similarly, samples were composited from two multi-effect
evaporators which also differed in effluent water qual-
ity.
The liquid streams chosen for the first day of sampling in-
cluded the well water, evaporator condensate, cooling tower blow-
down, influent and effluent streams from wastewater treatment,
city water, and barometric condensate. For quality control pur-
poses, the first five of these streams were chosen to be sampled
again on the following day. Unfortunately, the liquid samples
from the second day of sampling (17 August) were delivered 2 days
late by the shipper. Time permitted for the priority pollutant
samples to be recollected, but not for the duplicate liquid
streams. Parameters from these five streams which must undergo
analysis within 24 hours to ensure their integrity are BOD, TOC,
COD, and ammonia (see Table 40). The results for these param-
eters must be considered suspect and have been omitted from the
results.
The normal operation of the wastewater treatment system was
disrupted due to a pipe failure the morning of the second sam-
pling day (17 August). Repairs were made within 2 hours and
sampling efforts were resumed for the wastewater treatment
system. However, the concentrations measured for many of the
parameters in the wastewater influent were abnormally high,
indicating several more hours were necessary for treatment
operations to stabilize. Therefore, values for these samples
have been deleted from the results.
Gas Streams
The air effluent stream sampling was begun on the second day
after calibrating instruments, setting up sampling equipment, and
confirming sampling port locations for these streams. The first
parameters measured were particulate matter from the cyclone ef-
fluent stream which is associated with by-product dryers.
130

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TABLE 40. PRESERVATION AND PREPARATION REQUIREMENTS FOR
LIQUID STREAM PARAMETERS (148)
Preserva- Analysis
tion Preparation Time Quantity^1'
Analytical Parameter Technique Techniaue Limit Collected
Total Dissolved
Cool, 4°C
Filter
7 days

Solics




Volatile Suspended
Cool, 4°C
Filter
7 days

Solids



200 ml
Total Suspended
Cool, 4°C
Filter
7 days

Solids




Volatile Suspended
Cool, 4°C
Filter
7 days

Solids




BOD
Cool, 4°C

24 hours

Sulfates
Cool, 4°C

7 days
200 ml
Iodine
Cool, 4°C

24 hours

COD
Cool, 4°C
Acidify to
7 days



pH <2 with

200 ml

Cool, 4°C
H2S°2
24 hours

TOC
Cool, 4°C
Filter,
24 hours
200 ml


acidify to




pH <2 with




h2so4


Pesticides
Cool, 4°C


200 ml (glass)
pH

On-Site
6 hours
200 ml


Measurement


Cu, Fe

Acidify to

200 ml


pH <2 with




hno3


Benzene
Cool, 4°C


glass vial




(no air)
Priority Pollutants




Purgeables
Cool, 4°C


2 glass vials
Base/Neutrals
Cool, 4°C


750 ml (glass)
Cyanides
Cool, 4°C
pH 2 with
24 hours
200 ml


NaOH


Phenols
Cool, 4"C
Acidify to
24 hours
200 ml (glass)


pH <4 with




V°4


Metals

Filter,
6 months
200 ml


acidify to




pH <2 with
iron


(*) Every 2 hours for an 8-hour period.
131

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Mechanical difficulties were encountered with the organic vapor
analyzer (OVA) that day which prevented further sampling. Re-
pairs were made in time to sample the fermenter vent for ammonia,
the dryer cyclone effluent stream for total hydrocarbons (THC),
and the condenser vents on t-he dehydration column and stripping
column for benzene and THC the following day. On the last day,
the dryer cyclone effluent stream was sampled for ammonia, N0X_,
and SO2; the fermenter vent and condenser vents on the beer,
still, solvent extractor, rectifier, and fusel oil column were
sampled for THC.
There were several changes made in the collection and analy-
sis of air effluents. Inspection of the facility revealed that
the cyclones on the grain milling operations were in a closed-
loop system, thus preventing the collection of samples from the
cyclone inlet or outlet stream. Also, the condenser vent on the
flash cooler and the cyclone inlet for the by-product grain dryer
were physically inaccessible to the sampling team. In addition,
the separator vent and condenser vent for the stripping column
shared the same vent line as - the benzene makeup storage tank.
Total air emissions from these three sources are identified as
stripping column condenser vent effluents.
Six of the gas streams contained significant concentrations
of water and it was necessary to remove this water prior to total
hydrocarbon (THC) analysis. These streams included the cyclone
outlet stream on the dryer, solvent extractor, rectifier, and
fusel oil column. The water was removed from the stream by use
of a Perma-Pure® dryer which contains an osmotic membrane that
passes water vapor from the sample stream. The THC concentration
measured is therefore on a dry-gas basis.
The gas velocity of the dryer cyclone effluent was measured
at 22 points in the duct using an "S-type" pilot during the two
collection periods for particulate matter. The flow rate was de-
termined on a dry basis by removing the measured moisture content
from the process flow. The moisture content of the stream was
determined by weighing the impingers before and after the runs,
and then comparing the gain in weight with the metered gas vol-
ume.
The gas velocity of the carbon dioxide stream from the fer-
menter vent could not be measured. Values for the flow rate were
taken from plant records.
Gas velocities of the remaining streams (condenser vents on
the beer still, solvent extractor, fusel oil column, rectifier,
dehydration column and stripping column) were measured using a
self-contained and direct-reading velocimeter.
132

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The temperatures of all the streams except the fermenter
vent were measured using a dial thermometer. Since these streams
were atmospheric vents, the measured gas temperatures and atmo-
spheric pressure were .used in calculations to determine flow
rates at standard conditions.
Gas velocity measurements were made at each vent except the
fermenter - vent over -two 1-minute periods. -Readings were -taken
every 5 seconds over 1-minute intervals. This was done twice and
the two values were averaged to provide the flow rate. The ac-
curacy of these measurements is questionable, due to the very
erratic flow natures of the vents. Also, the flow rate from
these vents can be in either direction. The velocimeter
registered a zero reading if a reverse flow was occurring.
133

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98.	Nebraska Air Pollution Control Rules and Regulations (Ne-
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99.	Nebraska Domestic and Industrial Liquid Wastes Disposal
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100.	Nebraska Environmental Protection Act (Reissue Revised
Statutes of Nebraska, 1943, 1971 Supplement; as amend-
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101.	Nebraska Regulation of Disposal Sites Act (Sections 19-4101
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16, 1977).
102.	Nebraska Solid Waste Management Rules (Nebraska Department
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104.	Nebraska Water Quality Standards (Department of Environmen-
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105.	Nemerow, N. L., Theories and Practices of Industrial Waste
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18
19
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Perry, John H. Chemical Engineers Handbook. 5th Edition
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Resource Conservation and Recovery Act of 1976 (42 U.S.G.
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Roop, R. Dickinson, "Energy from Biomass: An Overview of
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1 28
129
130
Scheller, William A., "The Use of Ethanol -- Gasoline Mix-^
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141
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148

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APPENDIX A
FLOW DIAGRAMS AND MASS BALANCES FOR SELECTED ALCOHOL PLANTS
PROCESS EVALUATIONS
After reviewing the data collected in Task I, three alcohol
facilities were chosen for further study based on the following
criteria:
•	Product Type (methanol or ethanol);
•	Development status;
•	Product quality (beverage or fuel grade);
•	Plant design and availability of data.
Product Type
Based on information gathered concerning alcohol processes,
it was concluded that methanol/gasoline mixtures were inferior to
ethanol/gasoline mixtures for large-scale use as motor fuel. Ex-
amples of some problems methanol/gasoline mixtures entail are:
•	Methanol/gasoline mixtures have low tolerances for water
and exhibit phase separation at the ppm level of water
contamination. Ethanol/gasoline mixtures can tolerate
twice as much water as methanol/gasoline mixtures.
•	Methanol has relatively low energy content (about half
that of gasoline). Ethanol contains approximately 2/3
the Btu content of gasoline.
•	Addition of methanol to gasoline substantially increases
the Reid Vapor Pressure (RVP) of the resulting mixture
and might cause vapor lock. Ethanol does not increase
RVP as much as methanol.
•	Significant quantities of methanol in motor fuel might
necessitate carburetor modifications since it burns lean-
er (and thus may cause performance deficiencies such as
stalling, hard starting, and lean surge). Ethanol can be
utilized in concentrations up to 20 percent without car-
buretor modifications.
149

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Ethanol from grain or other biomass materials has the sup.-
port of an influential political force which will spur its use as
a motor fuel component. For example, the 1978 Energy Bill remov-
ed -the 4cVgallon federal tax from gasohol (mixtures containing 10
percent ethanol and 90 percent unleaded gasoline) which amounts
to a subsidy of 40
-------
Four fermentation alcohol plants in the United States ar^
currently manufacturing anhydrous, denatured ethanol. These fa-
cilities formerly produced beverage grade alcohol, but have re-
cently added a dehydration unit along with several processing
modifications to increase operating efficiency. Two of these fa-
cilities have been chosen for further study and are included in
Section 3. Other beverage alcohol plants in the U.S. are plan-
ning to add a dehydration unit to their facility and will -al'so_
provide ethanol for use in gasohol.
Plant Design and Data Availability
Although there are no grassroots facilities specifically de-
signed to support a gasohol industry, the plants considered in
Section 3 have many processing steps which are expected to be
present in future fuel grade alcohol plants. The three plants
chosen for further study in Section 3 will be drscussed below in
terms of their advantages and disadvantages with regard to oper-
ating schemes and data availability.
Plant I has been converted from a beverage plant to a fuel
plant and with the modification planned (removal of purifying
columns and perhaps continuous fermentation), will closely re-
semble a grassroots ethanol fuel plant. Because the waste
streams from the alcohol plant are combined with wastewater from
other on-site processes, proper sampling of this facility would
be difficult.
Plant II has added a benzene dehydration unit and begun pro-
duction of anhydrous ethanol; however, no other process modifica-
tions are currently under consideration. This plant has a segre-
gated wastewater treatment system which recycles wastewater
sludge back to the alcohol process, thereby eliminating a solid
waste disposal problem and increasing by-product output (distil-
ler's dried grains and solubles). This plant was chosen for the
sampling effort.
The third plant is the most modern ethanol facility in North
America. However, the facility is strictly a beverage plant and
has no plans for any modification which might alter the quality
of their product. Nevertheless, the plant could provide useful
data concerning processing steps they would have in common with a
grassroots ethanol fuel plant.
Alcohol Plant I--
Figure A-1 presents a flow diagram representing a beverage
ethanol plant which has been converted to an ethanol fuel plant.
Table A-1 gives the flow rates and compositions of the process
streams illustrated in Figure A-1 for Plant I.
151

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To Wastewater
Treatment
Carbon Dloxidts
Vet
Hilling
Grain
Flash
Cooler
Cooker
Water
Enzyme
Beer
Still
Ethanol
Scrubber
Centrifuge (29}
Dryer
Blowdown
DOO
Figure A-l. Flow diagram for plant I.

-------
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
TABLE A-l. MASS BALANCES PLANT I
Origin & Destination
Grain from storage to wet milling
Water (from cooling water) to wet
milling
Milled grain from wet milling fed
to corn sweetener plant
Product from corn sweetener
Partially saccharified starch
with protein to cooker
Stillage from beer still to cooker
150# steam to cooker
Mash, from cooker to flash, cooler
Condensate from flash, cooler to
wastewater treatment
Saccharifying enzyme to flash,
cooler
Mash, from flash, cooler to
fermenter
Carbon dioxide from fermenter
Yeast makeup to fermenter
Beer from fermenter to beer still
Overhead condensate from beer
still and feed to rectifier
S tream
Composition
Component
lb/hr
Wt :%
whole grain
50,400
100/0
water
235,200
100.0
milled grain
water
50,400
235,200
17.6
82.4
starch,
protein oils
water
23,400
109,200
17.6
82.4
starch/protein
water
27,000
126,000
17.6
82.4
solids
water
4,430
84,270
5.0
95.0
water
35,740
100.0
solids
water
31,430
210,270
13.0
87.0
water
126,930
100.0
enzyme
2,570
100.0
solids
water
34,000
119,080
22.2
77.8
carbon dioxide
13,725
100.0
yeast
4,000
100.0
solids
water
ethanol
11,470
117,550
14,335
8.0
82.0
10.0
ethanol
water
fusel oils
14,335
3,400
165
80.0
19.0
1.0
(continued)
153

-------
TABLE A-l. (continued)
Stream
Origin & Destination
16	Steam to beer still
17	Beer still bottoms to centrifuge
18	Rectifier overhead condensate
19	Fusel oils from rectifier
20	Rectifier bottoms to ww treatment
21	Overhead condensate from benzene
recovery column
22	Feed to benzene azeotrope column
23	Top layer from separator including
benzene makeup to benzene
azeotrope column
24	Benzene makeup to benzene
azeotrope column
25	Ethanol from benzene azeotrope
column
26	Bottom layer from separator to
benzene recovery column
27	Steam to benzene recovery column
28	Bottoms from benzene recovery
column to wastewater treatment
29	Supernatant from centrifuge to
evaporator or cooker
30	Supernatant from centrifuge to
evaporator
Component
water
solids
water
ethanol
water
fusel oil
water
water
ethanol
water
benzene
ethanol
water
benzene
ethanol
water
benzene
benzene
ethanol
ethanol
water
water
water
solids
water
solids
water
Stream
Composition
Ib/hr Wt %
49,915 100.0
11,470
163,900
14,335
600
105
60
752
647
175
550
1,150
8,320
158,050
3,890
73,780
6.5
93.5
96.0
4.0
65.0
35.0
2,800 100.0
752
47
175
15,087
647
175
1,253
158
7,855
77.2
4.8
18.0
94.8
4.1
1.1
13.5
1.7
84.8
40 100.0
14,335 100.0
47.8
41.1
11.1
100.0
100.0
5.0
95.0
5.0
95.0
(continued)
154

-------
TABLE A-l. (continued)
Stream	Origin & Destination
31	Condensate from evaporator
overhead to wastewater treatment
32	Evaporator bottoms to dryer
33	Centrifuge cake to dryer
34	Dryer feed from centrifuge
and evaporator
35	Water vapor from dryer to
scrubber
36	Distiller's dried grains and
solubles from dryer
37	Hot dry air from oil or natural
gas fired burner
Component
water
solids
water
solids
water
solids
water
water
solids
water
flue gas
Stream
Composition
lb/hr Wt %"
66,550 100.0
3,890
7,230
3,150
5,850
7,040
13,080
7,040
610
35.0
65.0
35.0
65.0
35.0
65.0
12,470 100.0
92.0
8.0
80,000 100.0
155

-------
Modifications which have been made include the addition of. a
benzene dehydration unit and removal of purifying columns. The
major impurities (primarily higher alcohols, also called fusel
oils) are. removed in a sidestream from the rectifier. If these
fusel oils are not removed from the distillation column, they
will build up in the rectifier and upset proper operation. Since
this plant produces fuel grade ethanol, the fusel oils can be
combined with the finished product.
Other alterations being considered by this plant include en-
larging the beer still to include rectification (eliminating the
need for a separate rectifier) and utilizing continuous fermenta-
tion (still a developing technology) to increase production.
Alcohol Plant I operates in conjunction with a corn sweet-
ener plant which utilizes some of the protein, oils, and starch
and provides a high sugar content feedstock for the alcohol pro-
cess. This situation is ideal since the corn sweetener products
are of relatively high value and a portion of unfermentable ma-
terial is removed from the alcohol plant feedstock.
The wastewater treatment facilities for Plant I are typical
for a fermentation alcohol plant and include extended aeration
and clarifiers. The wastewater from the alcohol plant is com-
bined with the wastewater from other on-site processes and,
therefore, a material balance could not be prepared for the
treatment facility.
Alcohol Plant II--
The flow diagram and material balances for Alcohol Plant II
are presented in Figure A-2 and Table A-2, respectively.
Alcohol Plant II is a beverage plant which produces neutral
grain spirits; a benzene dehydration unit has been added to one
of their distillation trains to produce anhydrous ethanol. The
addition of a dehydration unit is the only modification presently
planned by this facility which intends to remain primarily in the
beverage alcohol market. The dehydration units of Plant I and II
are similar except that Plant II routes the Benzene Stripping
Column overheads to the separator while Plant I returns this
stream to the Benzene Dehydration Column. The method employed by
Plant II is superior because it takes advantage of density and
solubility differences of ethanol, water, and benzene to promote
separation while the Plant I relies more on energy-intensive dis-
tillation.
Alcohol Plant II has a unique wastewater treatment facility
which routes sludge from the extended aeration pond to the dryer
for inclusion in the by-product feed. This essentially elimin-
ates solid waste disposal problems.
156

-------
Ul
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Protein
Extractor
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Cooker
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Whole Steam
Grain

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Flash
Cooler
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Converter
Tank

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Scrip-
B«p*r«ior
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beer
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Water
Steam
Water
100 X Ethanol
Cooling Water & Boiler Blowdovn
56
Evaporator
Flash Cooler
Condensate
Screens
Animal Feed
Atmosphere
1Z Solids
Extended
Aeration
Centrifuge
Centrifuge
Flue Oan
#-To River
Figure A-2. Flow diagram for Plant II.

-------
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
TABLE A-2. MASS BALANCES PLANT II
Origin & Destination
Flour and water from wet milling
Product from protein extractor
Flour feed from protein
extractor to cooker
Stillage from centrifuge
Whole grain, fresh feed to cooker
Steam to cooker
Mash from cooker to flash cooler
Flash cooler condensate to
wastewater treatment
Mash from flash cooler to
converter tank
Saccharifying enzyme to converter
tank
Cooled mash from converter tank
to fermenter
Yeast to fermenter
Water from fermenter
Mash from fermenter to beer still
Steam to beer still
Beer still bottoms to centrifuge
Beer still overheads to solvent
extractor
Stream
Composition
Component	lb/hr Wt :%
flour
139,950
75.0
water
46,650
25.0
protein,
starch,

oils
21,770
25.0
water
65,320
75.0
flour
24,880
25.0
water
75,630
75.0
solids
1,370
4.0
water
32,880
96.0
grain
2,750
100.0
water
27,100
100.0
solids
29,000
17.7
water
134,610
82.3
water
27,100
100.0
solids
29,000
21.2
water
108,010
78.8
enzyme
2,500
100.0
solids
31,500
22.5
water
108,010
77.5
yeast
4,500
100.0
water
13,725
100.0
water
105,500
81.0
ethanol
14,335
11.0
solids
10,450
8.0
water
39,400
100.0
solids
10,450
7.0
water
138,800
93.0
ethanol
14,335
70.2
water
6,000
29.3
fusel oils	100 0.5
(continued)
158

-------
TABLE A-2. (continued)
Stream
Composition
Stream	Origin & Destination
18	Recycled process water to solvent
extractor
19	Alcohol stream from fusel oil
column to solvent extractor
20 Total feed to solvent extractor
21	Solvent extractor overheads to
fusel oil column
22	Alcohol stream from solvent
extractor to rectifier
23	Steam to solvent extractor
24	Solvent extractor bottoms to
wastewater treatment/recycle
25	Steam to fusel oil column
26	Overheads from fusel oil column
27	Fusel oil side stream from fusel
oil column
28	Rectifier overheads to fusel oil
column
29	Fusel oil column bottoms to ww
treatment/recycle
30	Rectifier alcohol sidestream to
benzene dehydration column
31	Steam to rectifier
Component
water
ethanol
water
fusel oil
ethanol
water
fusel oils
ethanol
water
fusel oils
ethanol
water
fusel oils
water
water
water
aldehydes
water
fusel oil
water
ethanol
water
fusel oil
water
ethanol
water
water
lb/hr
Wt % -
175,000 100.Q
7,664
335
70
21,999
181,335
170
1,964
701
140
20,035
180,585
30
6,215
4,100
15
25
85
35
5,700
270
30
14,335
750
95.0
4.2
0.8
10.8
89.1
0.1
70.0
25.0
5.0
10.0
89.9+
150 (*)
5,800 100.0
100.0
100.0
37.5
62.5
70.8
29.2
95.0
4.5
0.5
4,676 100.0
95.0
5.0
13,900 100.0
(*) ppm
(continued)
159

-------
32
33
34
35
36
37
38
39
40
41
42
43
44
45
TABLE A-2. (continued)
Origin & Destination
Rectifier bottoms to
t reatment/recycle
Distillation columns bottoms to
wastewater treatment
Benzene dehydration column
overheads to separator
Separator top layer to benzene
dehydration column
Benzene dehydration column
bottoms (product)
Total separator feed overheads
from benzene recovery column and
benzene dehydration column
Separator bottom layer to
benzene recovery column
Benzene recovery column
overheads to separator
Benzene recovery column bottoms
to wastewater treatment/recycle
Supernatant from centrifuge to
cooker or evaporator
Supernatant from centrifuge to
evaporator
Centrifuge cake to dryer
Evaporator overhead condensate
to wastewater treatment
Evaporator bottoms to dryer or
animal feed
Component
water
water
ethanol
water
benzene
ethanol
water
benzene
ethanol
ethanol
water
benzene
ethanol
water
benzene
ethanol
water
benzene
water
solids
water
solids
water
solids
water
water
solids
water
Stream
Composition
lb/hr Wt.-%"
193,465 100.0
30,106 100.0
2,393
957
9,585
2,39 3
207
9,585
3,349
1,029
9,807
956
822
222
956
72
222
5,392
129,408
4,022
96,528
5,058
9,392
18.5
7.4
74.1
19.6
1.7
78.7
14,335 100.0
23.6
7.3
69.1
47.8
41.1
11.1
76.5
5.8
17. 7
750 100.0
4.0
96.0
4.0
96.0
35.0
65.0
90,495 100.0
4,022
6,033
40.0
60.0
(continued)
160

-------
46
47
43
49
50
51
52
53
54
53
56
57
53
59
(*
TABLE A-2. (continued)
aCream
Comuosicion
Origin & Dggr-i nation
Anlral feed from evaporator
Evaporator bottoms Co dryer
Centrifuge cake (wastewater
treatment) Co dryer
Total dryer feed
3oilar flue gas co dryer
Distiller's dried grains and
solubles from dryer
Dryer off gas co atmosphere
Total process water
Centrifuge 3-upernatant
wastewater treatment co
wastewacer treatment
Cooling water and boiler
blowdowu
Total feed co wastewater
treatment screens
"Wastewater from screens co
extended aeration
Treated wastewater from
ascended aeration
Solids from wastewater creacmenc
to centrifuge
Component"
solids
water
solids
vatar
solids
water
solids
water
air
wat er
solids
water
air
water
solids
water
solids
water
water
solids
water
solids
water
solids
water
solids
water
lfr/cir
300
1,200
3,222
4,333
50
960
3,330
15,135
162,260
12,780
3,320
725
162,260
27,240
55
243,250
5
4,550
60
908,050
60
908,050
5
902,550
35
5,500
wt ~Z
40.0
60.0
40.0
60.0
0.5
99.5
35.4
64.5
92. 7
7.3
92.0
3.0
35.5
14.4
227 (*)
99.9-
0.1
99.9
660,250 100.0
66(")
99.9+
66( * )
99.9-t
5.5 (*)
99.9-
1.0
99.0
PPffl
161

-------
Similar to Alcohol Plant I, Alcohol Plant II employs proces-
sing units upstream from the cooker to remove protein, oils, and'
fiber from the alcohol plant feedstock.
Alcohol Plant III--
The flow diagram and mass balances for Plant III, a whiskey-
distillery, are presented in Figure _A-3 and Table_A-3, respec-
tively.
The operators of this particular plant are primarily con-,
cerned with product quality and no modifications are planned
which would alter this quality. The flow diagram clearly shows
the additional processing units such as the purifying, aldehyde,
and fusel oil columns which typify such a facility.
There are no process units upstream of the cooker to remove
unfermentable materials as in Plants I and II. This, again, is
to preserve product quality. It also improves the value of the
Distiller's Dried Grains and Solubles (DDGS) which contain higher
amounts of proteins, oil and fiber.
162

-------
Water to
Wastewater
Tivai nuiit Carbon
Stoan
Cooker
Hill lug
Water
Water
Beer
Still
95 X Etliaool
5 Z Water
Fusel Oils
Water
Water
To
>0)
Centrifuge
Scrubber
Dryur
To Waatevater
Troatctant
D00
Figure A-3. Flow diagram for Plant III.

-------
TABLE A-3. MASS BALANCES FOR PLANT III
Stream
Composition
Stream
Origin & Destination
Component
lb/hr
-Wt X
1
Grain from storage to milling
grain
28,360
100-.0
2
Process water to cooker
water
85,080
100.0
3
Steam to cooker
water
28,150
100.0
4
Stillage to cooker
solids
water
1,135
36,680
3.0
97.0
5
Enzyme to cooker
enzyme
2,500
100.0
6
Mash from cooker to flash cooler
solids
water
32,000
149,910
17.6
82.4
7
Flash cooler condensate to
wastewater treatment
water
13,910
100.0
8
Mash from flash cooler to
fermenter
solids
water
32,000
136,000
19.0
81.0
9
Carbon dioxide from fermenter
carbon dioxide
13,900
100.0
10
Yeast to fermenter
yeast
5,235
100.0
11
Mash from fermenter to beer still
ethanol
water
solids
14,335
132,250
12,750
9.0
83.0
8.0
12
Beer still bottoms to centrifuge
solids
water
12,750
169,400
7.0
93.0
13
Steam to beer still
water
37,150
100.0
14
Beer still overheads to
purifying column
ethanol
water
fusel oils
14,335
3,460
140
79.9
19.2
0.9
15
Process water to purifying column
water
179,350
100.0
16
Total fresh feed to purifying
column
ethanol
water
fusel oils
14,335
182,830
140
7.2
92.7
0.1
17
Aldehyde and fusel oil columns
feed to purifying column
ethanol
water
fusel oils
4,560
765
15
85.4
14.3
0.3
18
Purifying column overheads to
aldehyde column
ethanol
water
aldetiydes
1,015
185
25
82.9
15.1
2.0
(continued)
164

-------
TABLE A-3. (continued)
Stream
Composition
:ream
Origin & Destination
Component
lb/hr
Wt "%'
19
Purifying column fusel oil
ethanol
1,880
76.1

sidestream to fusel oil column
water
470
19.0


fusel oil
120
4.9'
20
Alcohol/water sidestream from
ethanol
16,000
66.0

purifying column to rectifier
water
8,220
34.0


fusel oil
10
413(*!
21
Purifying column bottoms to
water
174,720
100.0

wastewater treatment



22
Aldehyde column bottoms to
ethanol
1,015
86.0

column
water
160
13.6


aldehydes
5
0.4
23
Aldehyde column overheads
aldehydes
20
44.4


water
25
55.6
24
Fusel oil column overheads to
ethanol
3,545
85.2

purifying column
water
605
14.5


fusel oil
10
0.3
25
Rectifier sidestream to fusel
ethanol
1,665
89.5

oil column
water
185
1.0


fusel oil
10
0.5
26
Fusel oil column bottoms
fusel oil
120
70.0


water
50
30.0
27
Rectifier overheads
ethanol
14,335
95.0


water
750
5.0
28
Rectifier bottoms to wastewater
water
7,285
100.0

treatment



29
Wastewater from purifying column
water
2,655
100.0

and rectifier



30
Supernatant from centrifuge to
solids
4,780
3.0

cooker and/or evaporator
water
154,615
97.0
31
Centrifuge supernatant to
solids
3,645
3.0

evaporator
water
117,935
97.0
32
Centrifuge cake to dryer
solids
7,970
35.0


water
14,795
65.0
(*) ppm
(continued)
165

-------
33
34
35
36
37
38
39
40
41
42
TABLE A-3. (continued)
Stream
Composition
Origin & Destination
Evaporator condensate to
wastewater treatment
Evaporator bottoms to dryer
Total dryer feed
Dryer recycle stream
Boiler flue gases to dryer
Distillers' dried grains and
solubles
Dryer off-gases to scrubber
Scrubber off-gases to
atmosphere
Make-up water to scrubber
Spent scrubber liquor to
wastewater treatment.
Component
water
solids
water
solids
water
solids
water
air
water
solids
water
air
water
air
water
water
water
lb /hr
Wt. %_
114,290 100.0
3,645
3,645
39,335
21,180
27,720
2,740
102,570
8,080
11,615
1,150
102,570
25,370
102,570
9,640
15,730
15,730
50.0
50.0
65.0
35.0
91.0
9.0
92. 7
7.3
91.0
9.0
80.2
19.8
91.4
8.6
100.0
100.0
166

-------
APPENDIX' B
SUPPORTING DATA FOR SECTION 3
ENVIRONMENTAL REGULATIONS
167

-------
TABLE B-l. CHARACTERIZATION OF THE EFFLUENTS FROM AN ALCOHOL FACILITY
cr>
oo
QuantiLy
Generated
Total
Solids
Suspended
Solids
BOD
£11
Stream
lb/day
gal/day
E£H
lb/da^
PPrc
lb/day

lb/day
Total

Scrubber Blowdown
657,000
78,800
2,600
1,708
760
499
1,040
683
31
5.0
Cooling Tower Blowdown
5,901,000
709,000
800
4,723
14
83
30
177
8
8.0
Boiler Blowdown
144,000
17,300
100
14
5
1
0
0
0
7.0
Evaporator Condensate
1,084,000
130,100
130
141
12
13
650
705
32
J.9
Plant & Equipment Washes
768,000
92,200
1,050
806
400
307
650
499
23
6.0
Rectifier Ualer
81,720
9,810
240
20
40
3
1,250
102
5
5.0
Sewerage Infiltration
144,000
17,300
NDA

NDA

NDA


NDA
Sanitary Sewage
96.000
11.500
750
72
200
19
200
19
	I
NDA
Total
8,880,000
1,066,000
843
7,484
104
925
246
2,185
100

NOIbS: NDA - No data available.
(continued)

-------
TABLE B-l
SOI.II) WASTES
Quantity
Generated
Stream	lb/hr
Sludge (effluent from wastewater treatment)	100
Power Generation Fly Ash	814
Bottom Asli - Haln Boiler	430
Collected Coal Duat	NDA
Collected Grain Duat	NDA
Flant Wastes (trash, boxes,	etc.) NDA
CT>
vO
Notes: NDA - No data available.
(continued)
AIR EMISSIONS
QuantlLy
Generated
Stream	lb/hr
Fermentation Vent
C02	14,000
Hydrocarbons	trace
Main Boiler - Coal-Fired (I23xl0& Btu/lir)
Flue Gases (wltli no control applied)	148,600
CO,	25,500
ll20	6,600
N2	105,200
02	9,800
N0x	86
S02	567
Fly asli	798
Unburned hydrocaibona	16
Dryer Furnace - Oil-tired	(46x10s Btu/lir)
Flue Cases - Scrubber Outlet:	235,500
C02	39,000
lljO	31,250
N2	161,000
02	4,050
S02	,13
N°x	5 5
Particulates	0.7
Fugitive Emissions	NDA

-------
TABLE B-2. SUMMARY OF NATIONAL AMBIENT
AIR QUALITY STANDARDS
L'ollutant
Particulate
Matter
Sulfur Oxides
Averaging Time
Annual (Geometric
Mean)
24-Hour*
Annual (Arithmetic
Mean)
24-Hour*
3-Hour*
Primary Standard
75 yg/m3
260 ug/m3
30 ug/m3
365 Jg/m3
Seconaarv Standara
60 ug/m3
150 yg/m3
1300 ug/m
(0.5 3om)
CO
3-Hour*
1-Hour*
10 mg/m3
(9 oom)
40 mg/m3
(35 opm)
10 mg/ii
(9 oom)
40 mg/m3
(35 ppm)
N02
Annual (Arithmetic
Mean)
100 ug/m3
(0.05 ppm)
100 yg/m3
(0 05 ppm)
Photochemical
Oxidants
1-Hour*
240 ug/m3
(0.12 ppm)
240 ug/m3
(0.12 ppm)
Hydrocarbons
(Non-Methane)
3-Hour**
(6 to 9 a.m )
160 ug/m3
(0.24 ppm)
160 ug/m3
(0.24 oom)
*The expected number of davs per calenaar year on which Che ozone level
exceeds Che given level must be less than or equal to L
**Not Co be exceeded more than once per year.
170

-------
TABLE B-3. AMBIENT AIR INCREMENTS
Maximum Allowable
Increase
(Micrograms Per-
Pollutant	Cubic Meter)
CLASS I
Particulate Matter:
Annual Geometric Mean	5
24-hr Maximum	10
Sulfur Dioxide:
Annual Arithmetic Mean	2
24-hr Maximum	5
3-hr Maximum	25
CLASS II
Particulate Matter:
Annual Geometric Mean	19
24-hr Maximum	37
Sulfur Dioxide:
Annual Arithmetic Mean	20
24-hr Maximum	91
3-hr Maximum	512
CLASS III
Particulate Matter:
Annual Geometric Mean	37
24-hr Maximum	75
Sulfur Dioxide:
Annual Arithmetic Mean	40
24-hr Maximum	182
3-hr Maximum	700
171

-------
-TABLE B-4. STATES' AIR REGULATIONS FOR FUEL BURNING EQUIPMENT.
Scare
CO
Z
Opacity
20
Ringelmann
Chart
30
Sew or
Existing
Source
Heac
Input
(10* 3tu/hr)
Particulate
Emissions
(lbs/104 3tu)
Suliur
Dioxide
Emissions
(lbs/10* 3tu)


Coal
Oil
Coal
¦311
All
0.10
0.501
i


Sources
1.00
0.30




10.00
0.27




100.00
0.13




230.00
0.12




500.00
0.10



lew
<230.00


1.20
0 30
Sources
>230.00


O.iO
0.30
Existing
tay
o
o
0.10

1.00*
aam1





Existing'
SL10.00*
I 00
0.10

1.00*

100.00
0 19
0 10

1.00*

2230.00
0.10
0.10

1.00*
lev
\ny
o
O
0. 10


Exlstiag-
Mec
Existing
Hew
"xlatlag'
£230.00
Any
Any
£230.00
>230.00
1.30
1.30
6.00
'iltrogen
Dioxide
Qusslons
(tbs/lO* 3tu)
Coal Oil
1.00*
0.70
0.90
0.30
0.30
1 Interpolation of the data for fuel burning equlpiaent shall be by use of the following equations
PE - 0.5	for n S 1.0
PE - 0 5 (PT)~ 26 for 1.0 < H i 500 0
PE - 0.1	for 500.0 i n
where: PE " Particulate emissions In pounds per (million Btu bene input.
FT ¦ Fuel input In million Btu pec hour.
*Kalaalon standard for CO Is ZOO ppm basis SO percent excess air for all sources with heat input*
>10.00*10* Btu/hr.
'CMMA - Located In the Chicago major metropolitan area.
*Thla represents the amount of emissions allowable when residual fuel oil Is burned. If distillate fuel oil Is
used* SO* emissions cannot exceed 0.3 lbs SO* per million 5tu of neat input.
sLocated outside the Chicago major metropolitan area.
'interpolation of the data for heat input ralues greater than 10 aillion 3tu per hour sut smaller than 220 aillion
3tu per hour shall be calculated by the following equation:
s 		LIS	
3s (Hs) 0.713
where: - Allowable emission standard in pounds per allllon 3tu of actual heat input.
9S • Actual heat Input, allllon 3tu per hour.
7S0z emission standards for fuel combustion sources located in the Chicago, St. Louis, and Peoria major metropolitan
areas (MMA), and any other MHA which has an annua1 arithmetic average sulfur dioxide level greater than 45 ug/a3
'nitrogen dioxide amission standards for fuel combustion sources located in the Chicago and St. Louis
(continued)
172

-------
TABLE B-4. (continued)
State Opacity
Klagelfflasn
Chart	
Sev or
Exiscing
Source
Heat
Iapuc
(10* 3tu/hr)
Particulars
Emissions
Ubs/10* 3tu)
Coal
Oil
Sulfur
Oioxide
CfflXSSlOQS
(ifra/10* 3tu)
Coal
Oil
^lerogen
Dioxide
Soissions
(Lbs/lO* 3tu)
Coal
Oil
IA
40
Existing
SMS A1
Existing
Saw
An y
Any
<150.00
150.00-
250.00
>250.00
0.6O
0.30
0.60
0.20
0.10
5.00"
6.00
6.00
1.20
2.SO
2.50
2.50
1.20
,
-------
TABLE B-4. (continued)
State Opacity
Rln g e loAtia
Chare	
MO
20
Sew or
Sxlsclng
Source
Exlscing-
rtec;
Mev-Hec^
All-Kmac1*
All-Slmac17
Ezlscing
Now
Ml
Sources
Heac
Input
(10* Stu/hr)
<10.OO1"
50.00
100.00
250.00
<1,0.00u
30.00
100.00
150.00
>0.35
<2000.00
<10.0011
50.00
100.00
220.00
<10.00"
50.00
100.00
250.00
>0.33
Particulate
"missions
(lba/10* 3tu)
Coal
Oil
0.60
0.40
0.33
0.26
O.iO
0.24
0.19
0.15
0.60
0.46
0.40
0.28
0.60
0.343
0.275
0.20
Sulfur
Dioxide
Eaisaloea
(lba/10* 3tu)
Coal
Oil
Nitrogen
dioxide
Emissions
(lba/10* Btu)
Coal Oil
3.00
2.30
3.00
13Fuel burning equipmenc emission standards In cha fCanims dry and Sc. Louis mecTopollcan areas.
l*Th« allowable parclculaca aalsslon races for heac Inpucs becveen 10 million BCu and 3,000 million Ecu per hour ara
determined by che following equaclon:
Z - 1.09
where: £ * Maxxaum allowable parclculaca emission race In pounds/mlllloo Ecu of heac lnouc.
Q • heac input in millions of Bcu per hour.
lsThe allowable parclculaca emission races for heac inpucs be ewe en 10 million and 1,000 million BCu per hour are
dacermlaed by Che following equation:
E - 0.30 (Q)~°"101
where: Z and Q are che same as above.
11 Sulfur dioxide emission llmlcaeions for che Kansas Clcy mecropollcan area.
i7Sulfur dioxide emlssloa llmlcaeions for che Se. Louis mecropollcan area*
"The a.'lovable parclculaca emission races for heac inpucs becveen 10 million and 10,000 million BCu per hour are
decarmlned by che following equation:
log Y - -0.23299 log X + 1.4091
where: 7 « Allowable emission races in pounds/millioa 3cu of Heac input.
Z ¦ Heac lnpuc in Beu per hour.
l,The allowable parciculace emission races for heac inpucs becveen 10 million and 2,000 million Btu per hour are
decermlned by che following equaclon:
log T - -0.3382 log X «¦ 2.1434
where: T and X are che sum as above.
174

-------
TABLE' B-5. PARTICULATE EMISSION STANDARDS FOR
EMISSION SOURCES
Particulate
Emission Standards
Process

Weight Rate
Emission Rate
(lbs/hr)
(lbs/hr)
50
0.03
100
0.55
500
1.53
1,000
2.25
5,000
6.34
10,000
9.73
20,000
14.99
60,000
29.60
80,000
31.19
120,000
33.28
160,000
34. sr
200,000
36.11
400,000
40.35
1,000,000
46.72
Interpolation of the data in this table for the process weight rates up to
60,000 lbs/hr shall be by use of the equation:
E = 3.59 P0-62	P < 30 tons/hr
and interpolation and extrapolation of the data for process weight rates in
excess of 60,000 lbs/hr shall be by use of the equation:
E = 17.31 P0-16	30 tons/hr < P
where: E = Emissions in pounds per hour.
P = Process weight rate in tons per hour.
(continued)
175

-------
TABLE B-5. (continued)

Particulate Emission
Standards

Process

Process

Weight Rate
Emission Rate
Weight Rate
Emission Rate
(lbs/hr)
(lbs/hr)
(lbs/hr)
(lbs/hr)
100
0.55
16,000
16.5
200
0.88
18,000
17.9
400
1.40
20,000
19.2
600
1.83
30,000
25.2
800
2.22
40,000
30.5
1,000
2.58
50,000
35.4
1,500
3.38
60,000
40.0
2,000
4.10
70,000
41.3
2,500
4.76
80,000
42.5
3,000
5.38
90,000
43.6
3,500
5.96
100,000
44.6
4,000
6.52
120,000
46.3
5,000
7.58
140,000
47.3
6,000
8.56
160,000
49.0
7,000
9.49
200,000
51.2
8,000
10.4
1,000,000
69.0
9,000
11.2
2,000,000
77.6
10,000
12.0
6,000,000
92.7
Interpolation of the data in this table for process weight rates up to
60,000 lbs/hr shall be accomplished by the use of the equation:
E = 4.10 P0-57
and interpolation and extrapolation of the data for process weight rates in
excess of GO,000 lbs/hr shall be accomplished by the use of the equation:
E - 55.0 P0-11 - 40
where: E = Rate of emission in lbs/hr
P ° Process weight in tons/hr
Does not apply to grain handling; also, if the director determines that a
process complying with the emission standards in this table is causing or
will cause air pollution in a specific area of the state, an emission stan-
dard of 0.1 grain/SCF 6f exhaust gas may be imposed.
(continued)
176

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TABLE B-5. (continued)
State	Particulate Fmission Standards
ILl

Emission
Rata

Emission
Race
Process
(lbs/hr)
Process
(lbs/hr)




Weignt Hate
Existing
New
Weight Rata
Exis tm|
Mew
(ibs/hr)
Sources
Sources 3
(lbs/hr)
Sources"
Sources 3
100
0.55
0 .55
50,000
35.40
14.00
200
0.37
0.77
60,000
40.00
15.60
400
1.40
1.10
70,000
41.30
17.00
500
1.33
1.35
80,000
42.50
18.20
800
2.22
1.53
90,000
43.60
19.20
1,000
2". 5 8
1.75
100,000
44.60
20.50
1,500
3.38
2.40
200,000
51.20
29.50
2,000
4.10
2.60
300,000
55.40
37.00
4,000
6.52
3.70
400,000
53.60
43.00
6,000
8.56
4.60
500,000
61.00
43.50
8,000
10.40
5.35
600,000
63.10
53.00
10,000
12.00
6.00
700,000
64.90
53.00
20,000
19.20
8.70
300,000
66.20
62.00
30,000
25.20
10.30
900,000
67.70
66.00
40,000
30.40
12.50
1,000,000
69.00
67.00
xDoes not apply Co grain handling and drying or com vet ailling.
2Interpolated and extrapolated values of the data m this table for process
weight rates up to 30 tons per hour shall be determined oy using the equation:
E » 4.10 ?a's7
where: E = Allowable emission rate in lbs/hr
? = Process weignt rate in tons/hr
and interpolated and extrapolated values of cne data for process weight rates
in excess of 30 tons per hour shall be determined oy using the equation:
E - 55.0 Pa*11 - 40
interpolated and extrapolated (up to process weight rates of 450 cons per
hour) values of the data in this table snail be aecermined by using cne
equation:
E - 2.54 p°-
and interpolacea and extrapolated values of "he"data of this cable for process
weight greater or equal to 450 cons per hour snail be determined using che
equation:
E - 24.3 P3*13
(continued)
177

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TABLE B - 5. ( continued)

Particulate Emission
Standards

Process

Process

Weight Rate
Emission Rate
Weight Rate
Emission Rate-
(lbs/hr)
(lbs/hr)
(lbs/hr)
(lbs/hr)
100
0.551
16,000
16.5
200
0.877
18,000
17.9
400
1.40
20,000
19.2
600
1.83
30,000
25.2
800
2.22
40,000
30.5
1,000
2.58
50,000
35.4
1,500
3.38
60,000
40.0
2,000
4.10
70,000
41.3
2,500
4.75
80,000
42.5
3,000
5.38
90,000
43.6
3,500
5.96
100,000
44.6
4,000
6.52
120,000
46.3
5,000
7.58
140,000
47.8
6,000
8.56
160,000
49.0
7,000
9.49
200,000
51.2
8,000
10.4
1,000,000
69.0
9,000
11.2
2,000,000
77.6
10,000
12.0
6,000,000
92.7
12,000
13.6


Interpolation of the data in this table for other process weights shall be
accomplished by use of the following equations:
Process weights < 30 ton/hr, E = 4.1 P0-67
Process weights > 30 ton/hr, E = 55 P0*11 - 40
where: E = Rate of emissions in lbs/hr
P = Process weight in ton/hr
(continued)
178

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TABLE B-5. ;(continued)
State	Particulate Emission Standards
Process
Weight Rate
(lbs/hr)
Emission Rate
(lbs/hr)
Process
Weight Rate
(lbs/hr)
Emission Rate
(lbs/hr)
2,000
4.10
30,000
25.2
2,500
4.76
40,000
30.5
3,000
5.38
50,000
35.4
3,500
5.96
60,000
40.0
4,000
6.52
70,000
41.3
5,000
7.58
80,000
42.5
6,000
8.56
90,000
43.6
7,000
9.49
100,000
44.6
8,000
10.4
120,000
46.3
9,000
11.2
140,000
47.8
10,000
12.0
160,000
49.0
12,000
13.6
200,000
51.2
16,000
16.5
1,000,000
69.0
18,000
17.9
2,000,000
77.6
20,000
19.2
6,000,000
92.7
Interpolation of the data in these two tables for process weight rates up to
60,000 lbs/hr shall be accomplished by use of the equation:
E = 4.10 P0-67
and interpolation and extrapolation of the data for process weight rates in
excess of 60,000 lbs/hr shall be accomplished by use of the equation:
E = 55.0 P0-11 - 40
where: E = Rate of emission in lbs/hr
P = Process weight rate in tons/hr
sDoes not apply to corn wet milling drying processes; these processes must be
equipped with control equipment to remove not less than 99.5 percent by
weight of all particulate matter in the dryer discharge gases.
(continued)
179

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TABLE B-5. (continued)

Particulate Emission
Standards

Process

Process

Weight Rate
Emission Rate
Weight Rate
Emission Rate
(lbs/hr)
(lbs/hr)
(lbs/hr)
(lbs/hr)
100
0.551
16,000
16.5
200
0.877
18,000
17.9
400
1.40
20,000
19.2
600
1.83
30,000
25.2
800
2.22
40,000
30.5
1,000
2.58
50,000
35.4
1,500
3.38
60,000
40.0
2,000
4.10
70,000
41.3
2,500
4.76
80,000
42.5
3,000
5.38
90,000
43.6
3,500
5.96
100,000
44.6
4,000
6.52
120,000
46.3
5,000
7.58
140,000
47.8
6,000
8.56
160,000
49.0
7,000
9.49
200,000
51.2
8,000
10.4
1,000,000
69.0
9,000
11.2
2,000,000
77.6
10,000
12.0
6,000,000
92.7
12,000
13.6


Interpolation of the data in this table for process weight rates up to 60,000
lbs/hr shall be accomplished by use of the equation:
E = 4.10 P0*67
and interpolation and extrapolation of the data for process weight rates in
excess of 60,000 lbs/hr shall be accomplished by use of the equation:
E = 55.0 P°-11 - 40
where: E = Rate of emission in lbs/hr
P = Process weight rate in tons/hr
If two or more units discharge into a single stack, the allowable emission
rate will be determined by the sum of all process weights discharging into
the single stack.
180

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TABLE B-6. STATE AIR REGULATIONS FOR FUGITIVE DUST AND
GROUND LEVEL PARTICULATE CONCENTRATIONS
5tate	Regulations
CO	No person shall emit or cause to be emitted from any source of
fugitive dust whatsoever, any particulate matter which:
•	at or from the source of said emission is of such a
shade or density on the property of emission origina-
tion so as to obscure an observer's vision to a
degree in excess of 20 percent opacity, or
•	is visibly transported off the property of emission
origination and remains visible to an observer posi-
tioned off said property when sighting along a line
which does not cross the property of emission
origination.
IL	No person shall cause or allow the emission of fugitive particu-
late matter from any process, including any material handling or
storage activity, that is visible by an observer looking generally
toward the zenith at a point beyond the property line of the
emission source.
No person shall cause or allow the emission of fugitive particu-
late matter from any process, including any material handling or
storage activity, in such a manner that the presence of such
particulate matter shown to be larger than forty (40) microns
(mean diameter) in size exists beyond the property line of the
emission source.
IA	No person shall allow, cause or permit any materials to be handled,
transported or stored: or a building, its appurtenances or a con-
struction haul road to be used, constructed, altered, repaired or
demolished, with the exception of farming operations or dust gen-
erated by ordinary travel on unpaved public roads, without taking
reasonable precautions to prevent particulate matter in quantities
sufficient to create a nuisance, as defined in Section 65 7.1 of
the Code, from becoming airborne.
(continued)
181

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TABLE B-6. (continued)
State	Regulations
KS	The provisions of other emission control regulations, notwith-
standing, no person shall cause or permit the handling, transport--
or storage of any materials or any other use of a premise in a
manner which has been demonstrated to allow sufficient quantities
of particulate matter to become airborne to cause a ground level
particulate concentration at the property line equal to or ex-
ceeding 2.0 milligrams per cubic meter above background concen-
trations of any time period aggregating more than 20 minutes
during any hour.
MO
No person may cause or permit the handling or transporting or
storage of any material in a manner which allows or may allow
particulate matter to become airborne in such quantities and con-
centrations that it remains visible in the ambient air beyond the
premises where it originates or that its presence may be found
beyond the premises where it originates, it has particulate matter
shown to be larger than forty (40) microns in size and which re-
sults in at least one complaint being filed with the executive
secretary.
No person shall cause, suffer, or permit the emission of any
particulate matter so as to cause concentrations of particulate
matter at any inhabited place to exceed any one of the following:1
Pollutant
Suspended
Particulates
(High volume
sampler)
Concentration
SO micrograms
per cubic meter
200 micrograms
per cubic meter
Soiling Index
(AISI paper
tape sampler)
0.4 C0II/1000
lineal feet
1.0 COH/1000
lineal feet
Remarks
6-month geometric mean
2-hour arithmetic averages for
not less than five two-hour
sampling periods within any one
year. No more than 3 samples
shall be taken during any 24-
hour period.
6-month geometric mean
8-hour arithmetic average
1This regulation shall apply throughout the state of Missouri except in the
City of St. Louis, and St. Charles, St. Louis, Jefferson, Franklin, Clay,
Cass, Buchanan, Ray, Jackson, Platte, and Greene Counties.
(continued)
182

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TABLE B-6. (continued)
State	Regulations
NB	Handling, Transporting, Storing. No person may cause or permit
the handling or transporting or storage of any material in a
manner which may allow particulate matter to become airborne in
such quantities and concentrations that it remains visible in
the ambient air beyond the premises where it originates.
183

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TABLE B-7. STATES' AMBIENT AIR QUALITY STANDARDS1
00
-P-
Sulfur Dioxide
Carbon Monoxide
State
CO
Primary Secondary Primary Secondary
lig/m3 	Mft/m3 nig/m3 mg/m3
IA
Category
1 II II I
AAM	2 10 15
24 lir max 5 50 100
3 lir ln.ix 25 300 700
0 03 ppm-
AAM
0.14 ppm-
24 lir
80-AAM
365-24 lir
0. 50 ppiii-
3 hr
1300-3 lir
9 ppm-8 hr
9 ppin-8 lir
35 ppm-1 lir
9 ppm-8 hr
35 ppin-1 hr
Nitrogen Oioxide
Annual Arithmetic
Mean (AAM)
tlg/m3
0.05 ppm
0 05 ppm-AAH
100
Photochemical
Ox idants
Mft/m3 max/1 hr
0.08 ppm
0 08 ppm
160
Nonmcthanc
Hydrocarbons
Ug/m3 mdx/l hr
(6-9 .).in.)	
0.24 ppm
0 24 ppm
160
Part lculntes
Primary Secondaiy
1'R^m3			
NondesignaLed areas
150-24 lir
Doslgnaled aieas
180-24 In
75-ACM
260-24 hr
75-ACM
260-24 hr
60-ACM
150-24 lir
60-ACM
150-24 hr
M0
53-AAM
365-24 lir
1300-3 In
53-AAM
365-24 hr
1J00-3 hr
9 ppin-8 hr
35 ppm-1 hr
100
160
60-ACM
150-24 hr
60-ACM
150-24 hr
NB 80-AAM
365-24 hr
1300-3 hr
9 ppm— 8 hr
35 ppin-1 hr
100
160
160
75-ACM
260-24 hr
60-ACM
150-24 hr
'Kansas has no Ambient Air Quality Standards for SOj , CO, NO , photochemical qxldantn, noninef li.ui" hydrocarbons, oi pari Ic.iilitis.
*	I

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TABLE B-8. ANALYSIS OF BEER STILLAGE
PH
Total Solids, ppm
Suspended Solids, ppm
BOD, ppm
Volatile Solids, ppm
Total Nitrogen, wt?0
Calcium
Magnesium (as MgO), ppm
Iron, ppm
Copper, ppm
4.1
47,345
24,800
34,100
43,300
0. 045
Trace
88
3
1
Sources: 14 and 30.
185

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