AIR POLLUTION  CONTROL

   TECHNICAL  REPORT
      ODOR CONTROL INVESTIGATIONS
      .



      B. N. Murthy and B, C, Eusebio




           DCS/RLB - 71-2



           March 1, 1971
                                          ^
   U. S. ENVIRONMENTAL PROTECTION AGENCY

        Air Pollution Control Office

        Division of Control Systems

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         ANNUAL RESORT

        Jan. - Dec. 1970
  ODOR CONTROL INVESTIGATIONS


 B. N. Murthy and B, C, Eusebio


         DCS/RLE - 71-2

         March 1, 1971
   Research Laboratory Branch
  Division of Control Systems
        Cincinnati, Ohio
ENVIRONMENTAL PROTECTION AGENCY

  Air Pollution Control Office

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                          SUMMARY







The odor control investigations in the Control Device Development Section




include both in-house and contract-support research work for the develop-




ment of suitable devices & processes for control of odorous emissions from




stationary sources.  DPCE started the investigations in 1968 with a lit-




erature survey on the state of the art of odor control technology, which




resulted in a report including recommendations for research and develop-




ment to be supported by DPCE.







The in-house work during 1970 consisted of laboratory studies aimed at




development of suitable wet-scrubbing reagents for odorous compounds




representing emissions from stationary sources.  Two compounds in each




of three groups of odorous emissions (mereaptans, amines and aldehydes)




were treated separately with several of the possible aqueous scrubbing




reagents under identical conditions, for comparison of the reagent




capabilities for absorption of odors from air.  The tests enabled the




identification of specific reagents having the maximum scrubbing




efficiency for each odorant species.  Detailed kinetic studies to deter-




mine the optimum operating conditions and design data for scrubbers




have been planned.







A contract project for studies on the adsorption of odorants on activated




charcoal was started during the year at Kansas State University.   The




studies are aimed at determining equilibrium adsorption conditions and




deriving mathematical models useful for the design of large scale ad-




sorption control devices for odor control.   Literature survey and ap-




paratus construction were in progress at the end of 1970.

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                        INTRODUCTION


DPCE started the odor control investigations  in 1968,  with a liter-

ature survey on the state of the art of  odor  control technology.   The

survey resulted in a. report which included recommendations for research

on odor control to be supported by DPCE  (Appendix A),


Based on the recommendations, the in-house odor control project aimed

at development of suitable wet scrubbing was  started in late 1969.  Odorous

compounds representing those present in  the emissions  of the most object-

ionable stationary industrial sources were selected  for the studies.  A

laboratory study was planned to determine in  the in-house laboratories,

the most promising set of reagents which could economically absorb

and remove odors in wet scrubbers.


Besides wet scrubbers, the control devices which were  identified as

requiring detailed investigations for improvement and  adaption to

odor control were:

    adsorption units
    catalytic converters
    afterburners
    combinations of control devices


A contract for Fundamental studies on the adsorption of odorants on

activated charcoal was signed with Kansas State University.

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                         DISCUSSION


In-house screening tests.

An experimental bench-scale apparatus including gas purifiers, metering

devices, temperature controls, absorption section and sampling ports,

was constructed.  A schematic design of the screening test system is

shown in Fig. 1.  The entire test system was set-up inside a large fume

hood to prevent odor pollution episodes in the laboratory.  An adsorption

filter was installed in the fume discharge duct which removed odors

from the fume hood.


The following odorants were selected for studies on the comparative

efficiencies of their removal from air by adsorption in several reagents:

     Odorants                         Common Industrial Sources
     Organic sulfur compounds-        Paper and pulp , agricultural chemicals ?
     butyl and methyl mercaptans      plasticizers , rubber products

     Nitrogeneous compounds           Fish processing industries, rendering
     - mono, di and tri methyl        plants
     Aldehydes                        Rendering plants, Incinerators
        Butraldehyde                  plastics
        Propionaldehyde
        Iso-valeraldehyde

From a knowledge of the chemistry of the odorants, and from the literature

survey, the following reagents were selected for experimental studies on

odor adsorption:

     a) alkalis
              - sodium hydroxide
              - calcium hydroxide
              - sodium carbonate

     b) acids
              - hydrochloric
              - sulfuric
              - sulfamic

     c) oxidizing agents
              - potassium permanganate
              - sodium and calcium hypochlorices

     d) other reactants
              - bisulfites

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The inlet concentration of each odorant in the air stream was  held

constant at 5000  ppm.   The reagents were compared at concentrations

ranging from 0.5 to 5 percent in water.


Analysis of the odorant before and after treatment with the reagent

was by gas chromatography-   Suitable combinations  of column type,

temperature, and detector were developed for  the analysis of each

odorant.  The reagents  were analyzed by standard wet chemical methods.


The complete results of the screening tests will be reported in a

paper being prepared for publication.  Some  typical results are shown

in Figs. 2, 3, and 4.  The following main observations have been made

from the screening test results:

     * Amines are efficiently removed by hydrochloric or sulfuric  acid.

     * Sodium hydroxide is the best scrubbing reagent for mercaptans,
       while calcium hydroxide slurry is a promising scrubber from the
       economic aspect.

     * Aldehydes are scrubbed best by sodium  and calcium bisulfites.

     * Potassium permanganate is a uniform scrubber for all the odorants,
       but is not the most efficient for any  odorant.  (Efficiency of odor
       removal was defined as percent of inlet odor absorbed by the same
       volume of reagent under identical conditions ,of contact time
       and reagent concentration.)

     * The efficiency of potassium permanganate depends oil  the pH of the
       solution, and is maximum in the pS range of 8 to 10.


The effect of operating conditions on the rate of  odorant removal will

be studied in detail with the best reagents  for each type of odorant.

Mathematical models useful for the design of  wet scrubbers  for odor

control will be derived from the kinetic studies.

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Program Plans

A proposed 5-year program plan for odor control projects to be conducted

in-house and by contract was prepared.


The in-house projects identified will include:

     a) Kinetic studies for odor control
     b) Pilot scale wet-scrubber development studies
     c) Semi-pilot scale adsorption studies for odor control
     d) Catalysis and afterburner  development
     e) Development of combined two-stage control devices and optimization
        studies
     f) Design and development work for odor control demonstration


Contract projects identified were:

     a) Odor adsorption studies using activated charcoal
     h) Selective sorption device development
     c) Odor control devices system study
     d) Follow-up R & D studies from odors control and related system studies
     e) Economic analysis and development of prototype odor control programs
     f) Demonstration studies

Procurement plan for the system study project to be supported on contract

is being prepared and a strong recommendation to fund the study during

FY72 will be made,


Existing Contract Activity

The in-house literature survey on the state of the art of odor control

had revealed the need for developmental work on adsorption control

devices as a high priority project.


A project was initiated with the contract signed with Kansas State

University for conducting fundamental studies relating to equilibrium

conditions and kinetics of adsorption of odorants in dilute concentrations

appearing in the emissions of stationary sources.  The detailed work plan

is attacked as Appendix B.                              '

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Literature survey,  experimental  apparatus  construction,  arid  calibration




are in progress.   The  contract will be  completed  in  September,  1972-

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                        CONCLUSIONS


The state of the art survey on odor control has pointed out the urgent

need for research and development work in the following areas:

     * Wet scrubber development
     * Adsorption
     * Afterburners and catalysis
     * System study on odor control devices
     * Optimization and engineering economic studies of combined two
       stage systems

In-house screening tests have shown that the following combinations

of odorant-reagent require detailed investigations for wet-scrubber

development:

     Mercaptans - Sodium and calcium hydroxide
     Aldehydes  - Sodium and calcium bisulfites
     Amines     - Hydrochloric and sulfuric acids
     All odorants - Potassium permanganate

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                           RECOMMENDATIONS

1. Follow-up work to the screening tests should be conducted in-house.

   Kinetic studies for odor control by gas-liquid contacting should be

initiated to develop mathematical models correlating operating

variables with rate of reaction.   Mass-transfer effects in the exper-

imental system should be kept at  the least rate-limiting level to

enable the determination of chemical reaction steps.

   The follow-up studies on wet-scrubber development will use the

results of the kinetic studies for developing optimum scrubber designs

for efficient and economic odor control systems.

2. Semi-pilot and pilot scale studies on adsorption and regeneration

should be conducted to determine  the effect of fluid dynamic conditions

on power requirements and material costs.

   The mathematical models developed from fundamental laboratory studies

should be used in the design of pilot scale fixed and fluidized bed

absorbers.

3. Though activated charcoal is widely used as an adsorbent for odor

control, it is a poor adsorbent for some odorants.   Selective adsorbents,

either through modification of activated charcoal or by investigation of

other surface active materials, should be developed for efficient odor

control in specific cases.   Examples of odorants  not effectively con-

trolled by activated charcoal are:

   Hydrogen sulfide
   Carbonyl sulfide
   Acetaldehyde
   Amines

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4.   A system study on the present application of odor control devices




and their limitations is needed to define the problems with existing




control devices, and to identify research and development needs for




eifective odor control.  The potential of existing control technology




for odor control applications should be investigated.

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                                                    Purge
Purified Air
                                    Mixer I
                                                                                      Mixer  II
                                                                                                Test Scrubber
                                                                              G. L, C.
                                                        Fig  1
                           SCREENING  TESTS  -  SCHEMATIC DESIGN OF TEST SCRUBBER - BENCH SCALE

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                                                                             mlt 3-10-70
                          0.5 %  KMn04
                                 ph 10
                                        8
10
12
14
Time (min.)
                                     Fig. 2

                         BUTYL MERCAPTAN SCREENING TESTS
16

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                                                                              MLT 2-5-70
Time (min.)
                                          Fig.  3




                               DIMETHYLAMINE SCREENING TESTS
                                                                                L_	L

5
10
15
20
25
30
35
40

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                                                                                        mlt 5-19-70
100
                                                        5% Ca(HS03)2
                                               2% KMn04 ph 10
                                                         w/  TCP
                                     5% KMn04 ph 10
                                         w/  TCP
                                        1% KMn04  ph 10

                                                 w/  TCP
                              1% KMn04 ph 10

                                      w/  TCP
                                               Borax 5%
                                               CaOCl2l% & 5%
                                               Ca(OH|  1% & 5%
                                               Dem. Dist. H 0
                                               HC1 1% & 5%
                                                     5%
                                               H2S04 1% & 5%
                                               NaOCl 1%
                                               NaOH  1% & 5%
                                               Na2C03 1% & 5%
                                               Sulfamic Acid 5%
          Time  (min.)
 6            8           1Q



BUTYRALDEHYDE SCREENING TESTS
                                                                                                   16

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      APPENDIX A
ODOR CONTROL RESEARCH

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A State-Of-The-Art Report and Research Recommendations
                 ODOR CONTROL RESEARCH
                      March, 1969

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                           SUMMARY
This report is a review of the state of technology for odor control and
evaluation.  The emission of odorous compounds forms a significant
portion of the air pollution problem.  It has been established that ob-
jectionable odors produce nausea, disturb sleep,  and reduce property
value.

Odor surveys indicate that the most common odor emission sources
are chemical and pulp manufacturers, petroleum and mineral refin-
eries, and food stuff waste product and animal rendering industries.

The technology of odor evaluation and control has not advanced to keep
pace with the growing problem.  No suitable  method or instrument is
available for measuring odors objectively.  Odor measurement tech-
niques presently being used are  mainly subjective.  Consequently, there
is a marked deficiency of quantitative information on odor emissions
from  industrial sources.

Techniques that can be used for  odor control are ventilation, absorption
chemical reaction,  process  changes, odor  modification, combustion,
and scrubbing. Of these, scrubbing offers the advantage of not being
highly specific to particular odorous emissions.

Research needs for the development of scrubbers to control odors are
discussed in  this summary report.   The report recommends that simple
odorous systems amenable to accurate analysis be selected initially.
Gas chromatographic equipment will be used for analysis of odorants.
The effect of operating variables on the efficiency of odor control will
be studied on a bench scale.  Results from these studies will be used
to form the input for pilot-scale scrubber studies.

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                         INTRODUCTION
One of the major uncontrolled air pollution problems is the emission of
odorous  compounds  into the atmosphere as a result of industrial activity.
Although gross atmospheric pollution in the form of smoke and dust has
been subjected to appraisal,  regulation, and statutary restriction, at-
tempts to control odors  have been highly complicated as a result of the
lack of uniform standards for measurement and classification of odors.
The magnitude of the overall odor pollution problem, as indicated by
the number of complaints about odors in ambient air surrounding indus-
tries, is increasing.

Odor is  defined as the characteristic of a substance that stimulates the
sense of smell, either pleasantly or unpleasantly.   The substance is
usually  airborne.  V/hen a solid or liquid gives  out an odor, the stimulus
is caused by the volatile molecules from the substance reaching the
sensory  nerves in the nose.

The relationship between the physical and chemical property of a sub-
stance and its odor quality has not been definitely established. Our
understanding of the sense of  smell is considerably less advanced than
our understanding of .other senses.  Attempts to  classify odors accord-
ing to molecular structure have not been very successful.   For instance,
aldehydes,  carbonyls, sulfur  compounds,  and hydroxy compounds cause
certain  typical smells, but take on entirely different characteristics at
various  concentrations  in air.  The odor of a mixture of odorous com-
pounds cannot be predicted from a knowledge of their individual odors.
The problem of classifying odors in terms of basic types is further com-
plicated  by psychological and  physiological factors.  An odor  that is of-
fensive to one person may be  tolerable  or  even pleasant to another.
But some smells fall definitely into the class of offensive odors.   These
include the putrefractive and fecal odors and some chemical odors that
are generally considered objectionable.

Until recently, odors were considered  something inevitably present
around industrial areas and few attempts were made to control them.
It has now been established that objectionable odors produce nausea,
disturb sleep, and reduce property value.    Some odors, like  emissions
from acrylate industries, are toxic even at low concentrations. 3  Al-
though ail industrial odors are not inherently harmful by nature, some

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 authorities believe that many odors may adversely affect public health^
 by causing an ionic imbalance in the atmosphere.  The presence of ex-
 cessive positive ions in air irritates mucous membranes, interferes
 with ciliary activity, and may increase general susceptibility to viral
 infection.'*

 Since industrial odors are a definite part of the overall air pollution
 problem, people concerned with the design, supervision, or administra-
 tion of  chemical plants should be familiar with the latest techniques avail-
 able'for controlling odors.  The purpose of this report is to review the
 state-of-the-art regarding odor evaluation and control methods and to
 make recommendations for a plan of research that will lead to the devel-
 opment of effective odor control techniques.
                        SOURCE OF ODOR

 Before an effective odor control program can be launched, the sources
 and nature of odorous emissions must be identified.  At present, there
 is a marked deficiency of published literature on the quantities, types,
 and concentrations of odorous emissions.

 In 1955 an opinion survey was conducted by Pendray and Company in
 67 major industrial cities. 5  Members of the communities v/ere ques-
 tioned about the sources  of odors.  This survey resulted in an estimate
 of the qualitative  nature of the problem, and indicated that the most
 common sources  of odors were the chemical manufacturers (Appendix A).

 More recently, in 196S the U.S. Public Health  Service conducted an odor
 survey in the St.  Louis communities bordering Missouri and Illinois.
 This survey again was a  qualitative assessment of the frequency and ob-
 jectionability of odors as sensed in ambient air by volunteers  geograph-
 ically distributed over the area. The survey showed that 80 percent of
 the chemical odors and 98 percent of the animal odors  (from rendering
 plants and stockyards) were considered to be objectionable (Table 1).

 The magnitude of the odor problem and  an estimate of the quantity of
 odorants to be removed at their source  can be determined by the ob-
 jactionability, odor threshold, and physiological effects of odors at
 ambient concentrations.  An objectionability scale ranging from "like
 extremely" to "dislike extremely" has been proposed by Turk^ to
 determine subjective reactions to odors.,  Objectionability alone cannot
be a sufficient criterion for control.   For example, hydrogen sulfide at
 concentrations sufficient to produce harmful effects loses its character-
istic offensive odor and produces a pleasant smell.  The characteristic

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smells  and odor thresholds for some of the commonly occurring pol-
lutants  are given in Table 2.4   The odor threshold for an odorous sub-
stance in the atmosphere is the minimum concentration that can be
detected by the human sense of smell.

In this review the common sources and compositions of odorous emis-
sions have been compiled from the literature and are listed in Appendix
B.  To  assess the relatrve contributions of the sources of air pollution,
the major types and quantities of pollutants emitted have to be classified.
The U.S. Public Health Service has published a compilation of air pol-
lutant emission factors,8 along with quantitative estimates of a few
odorous emissions. An emission factor is defined as the statistical
average of the rate at which pollutants are emitted from the processing
of a given quantity of raw material.  We may conclude from the study
of emission factors that the major chemical  source contributing to the
odor problem is the pulp and paper industry. The  characteristic odor
from a  pulp mill results mainly from a group of organic sulfur com-
pounds  of which the most important are methyl rnercaptan and its oxi-
dation products,  dimethyl sulfide  and dimethyl disulfide. 10

A survey of the odor complaints received by the Intercommunity Air
Pollution Control Program of the  city of Cincinnati indicated that most
of the complaints were  about odors from rendering plants, asphalt proc-
essing, and plastics industries.  No quantitative information on these
sources is available, however.

As part of its contract program, the Division of Economic Effects Re-
search of the National Air Pollution Control  Administration is conduct-
ing a study of the odor problem  in the nation in terms of sources,
description of odorants  (character, acceptability,  and other measures),
population- affected, and geographic distribution. ^  The study is aimed
primarily at the promulgation of air quality criteria.  Phase I of the
study is expected to identify the industrial processes and other sources
and describe major odorants.  Phase n includes an estimation of the
socio-economic impact  of  odors on the  community.  There is a great
need for quantifying the type of data expected to be  obtained in the study
mentioned above, so that the results can be used to develop control
techniques.

                     ODOR MEASUREMENT

The most effective  odor control methods are those  that prevent the re-
lease of odorous pollutants into the atmosphere.  Accurate assessment
of the odor problem and control equipment performance requires adequate

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techniques for measuring odors over a wide range of concentrations.  At
this time,  however, there are no fully satisfactory techniques for deter-
mining the character and  intensity of an odor.  This defficiency is undoubt
edly due in part to the lack of a satisfactory theory or even a-working
hypothesis covering the physiology, psychology, physics, chemistry,
and other aspects of the sense of smell.4

                v,
Measurement of Character and Intensity  of Odors

Some attempts have been  made in the past to characterize odors in terms
of basic  odor qualities.  The number of suggested basic odor types varies
from four upwards.  Crocker and Henderson*2 have used (1) fragrant,
(2) sour  (acid),  (3) burnt, and (4) goaty (caprylic).  The  object of this
kind of classification is to simulate an odor by mixing the basic types.
Henning1^  has suggested six basic types:  (1) spicy, (2) flowery,  (3)
fruity, (4)  balsamic (resinous), (5) burnt (empyreumatic), and  (6)foul
(offensive). Zwaardemaker- and others  have suggested from six to
eighteen basic odor types.  For practical use in the development of con-
trol technology,  none of these classifications has been generally accept-
able.

Most industrial odors are complicated mixtures of several chemical
components.  Since  instruments have not been perfected  to analyze odors
objectively, subjective evaluation by human observers  is often used to
estimate the character and intensity of industrial odors.  There are
mainly two methods by which the subjective (or sensory)  evaluation is
practiced:  (1) dilution and (2) suprathreshold or matching standard. *
In both methods  the intensity of an odor is measured in terms of 'odor
units'.  An odor unit is defined as the amount of odor necessary to con-
taminate 1  cubic foot of clean odor-free air to the threshold level.13:14,15
The number of times a given volume of the  sample gas  has to be diluted
with clean  odorless air to bring it to the  threshold level  (detected by 50
percent of  a panel of observers) is the value of the intensity in odor units.
The product flow rate times the odor intensity gives the rate of odor
emission.
Dilution Methods

Four major techniques are used to apply the "dilution" method of meas-
uring odor intensity in terms of odor units:

    1.   Cdorant air mixture with odor-free air in a container is brought
to an opening and sniffed.

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     2.   Part or all of the diluted mixture in a container is injected into
the nose.

     3.   The diluted mixture is ducted into a hood or chamber enclosing
the observer or only his face.

     4.   Odor-free and odorous air are inhaled in controlled proportions.


Of these methods, those in which the nose is immersed in the diluted
mixture give more accurate results than the injection or inhalation
method, because  in the immersion method the dilution rates and the rate
of odor delivery are exactly controlled by an unbiased operator. In the
injection method the panel member himself controls the rate of release,
the rate of injection, and the amount of inhalation. Also, it is impossible
to measure dilution by air that is displaced by the sample injected into
the nose.

Several devices for diluting gases for odor  measurement have been de-
                     " C 9 v                                          99
scribed in literature. i°~<"  Among these, the ASTTvI syringe technique-^
is widely used to  measure the strength of odors at effluent sources for
rough evaluations of the performance of control devices. The method
consists of drawing the odorous gas into a graduated  I00-ml syringe,
sampling it into a 2-ml syringe, and diluting it with odor-free air in
another 100-ml syringe.  A special sampling and diluting device is con-
structed for  the method from standard  hypodermic needles, which fit the
syringes.  The method is simple and gives  rapid approximate measure-
ments of odor intensity.
Matching Standard Methods

For the matching standard method,  a set of standards is calibrated to
indicate  objectionability and odor intensity on a scale.  Odor ants of
known concentrations are prepared as standards.  A nine-point scale of
the type  shown in Figure 1 was used by Duffee and co-workers1 to rep-
resent both objectionability and intensity.

An advantage of this method is that a concentration above the threshold
level can be directly matched against a standard mixture.  The method
is rapid,  but not very accurate since the intensity of odor from a com-
plex mixture is  easily affected by extraneous  factors like impurities
(even in traces), humidity of ambient air, and temperature.

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None           Slight           Moderate          Strong        Extreme
I	i	i        i        i   	|	I	i	   I
                             Figure 1
 Analytical Methods
 For developing or evaluating a control device, the best method of odor
 measurement is one that gives absolute  concentrations of odorous com-
 pounds in emission streams.  The analytical methods used for measure-
 ment of odorant concentrations are chemical or instrumental.  In many
 practical situations the composition of the odorous effluent can be deter-
 mined from a knowledge of the chemistry of the process or by analysis
 of emission samples. The odor  intensities of pure compounds have
 largely been found to follow the Weber-Fechner equation:1
                      P   =   K log S

               where  P   =   odor intensity

                      K   =   a constant

                 and  S   =   concentration of the odorant in air


For a mixture of compounds whose odor threshold data are available
through previous determinations,  gas  chromatographic analysis has been
successfully employed to estimate the odor intensity directly. 20-26 Q^LS
chromatography offers  an accurate method for analyzing complex mixtures
over a wide range of concentrations.
   -«» *
In some cases, a correlation between the concentration of a particular
constituent and the odorant  concentration or odor intensity can be estab-
lished.  An example of the application of this  approach involves the use
of devices to measure the concentration of carbon monoxide as an index
of the intensity of domestic incinerator effluent odor. 23  This approach
assumes a constant relationship between the components of the effluent
stream.
                        ODOR CONTROL

The development of devices specifically suitable for odor control has
not received sufficient attention in the past because of the diverse nature
of the problem.  The total quantity of gaseous emissions that must be

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 handled for the removal of odorants usually is large and results in high
 energy consumption and equipment costs.  Thus, the choice of a partic-
 ular odor control method depends on economic as well as technical con-
 siderations.

 There are four major ways to control odors;

     1.   Ventilation and diffusion.

     2.   Chemical conversion - combustion, chemical reaction, or
         change of process.

     3.   Odorant  capture - adsorption and absorption.

     4.   Masking or counteraction.
                ^            i


 Ventilation and Diffusion

 Ventilation is the  most common method of removing odorous air from en-
 closed spaces.  Industrial effluents are often diffused through stacks  into
 the atmosphere so that the odorous effluent is substantially diluted and
 reduced to below the threshold level in the ambient air.  This method
 cannot be successful if a large quantity of odorant is discharged or if the
 quality  of the outdoor air is unsatisfactory.


 Chemical Conversion

 Combustion is  the most commonly used method for odor control.   This
 method of control can be attained by direct incineration or,catalytic oxi-
 dation.  Direct incineration is usually accomplished by supplementing the
 odorous effluent with a fuel such as natural gas to provide incineration
 temperatures of 1200 to 1500°F. Odorants can be incinerated at sub-
 stantially reduced temperatures (600-900°F) if combustion catalyst is
used.  Oxy-cat Company^ ^^ developed catalysts to reduce the inciner-
 ation temperature of odorants to less than  600°F.   The main advantages
 claimed for the catalytic combustion method are low energy requirement
and nearly complete elimination of odors.  For both modes  of incineration
however,  when the concentration of combustible odorant in the effluent
stream  is low, the need to heat the large quantity of admixed air and
water vapor to the combustion temperature of the odorant makes incin-
eration  economically unattractive.

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 A number of processes employed by industries fall in the category of
 chemical reaction. Examples include the kraft pulping industry, where
 sulfate black liquor is oxidized to prevent the emission of mercaptans
 and hydrogen sulfide into the atmosphere. 31,32

 Scrubbing may be used to remove odorous pollutants from a gas stream
 by condensing or absorbing the pollutants  in a liquid.  Water is widely
 used for this purpose.  If an odor ant can be  reacted with a liquid to form
 soluble compounds or precipitates, chemical reaction accompanying
 correlation or adsorption completely removes odors. Examples of
 aqueous scrubbing include the work of Borger,36 wno has described
 the development of a method for successfully eliminating dimethylamine
 odors by scrubbing with water and dilute acid in absorption towers.
 Many odorous pollutants can be reacted with aqueous permanganate solu-
 tion to eliminate the odors. 33 This method  is economically applicable
 under conditions where effluents with high moisture contents are to be
 treated.  Rendering plant odors can largely be controlled by use of scrub-
 bing devices.35

 Essentially  all kinds  of scrubbing equipment (spray towers ,  cyclone
 scrubbers,  packed beds, venturi, etc.)  can work at high efficiencies
 when the odorant is absorbed easily. If the  reaction or solubility in the
 liquid is slow, packed towers or plate towers provide the residence time
 needed to achieve the  required mass transfer.  Designs  using free  liquid
 jet or spray are  useful when simultaneous adsorption of odorous compo-
 nents and precipitation of solids are  required.  Packed towers and  tanks
 are not suitable for this purpose, however, because the  solids remain
 suspended.  In general, pressure drop is high in plate towers and agitated
 tanks, moderate in packed towers, and low in spray towers and cyclone
 s crubbers.

 The'advantage of using scrubbers is that large quantities of odorous ef-
 fluent can be handled continuously and economically.
Odorant Capture

Active carbon is widely used to adsorb odorous components from air.
When the carbon is saturated with the odorous component, it is deacti-
vated and must be reactivated.  Carbon adsorption is used to  control
enclosed atmospheres and to eliminate solvents and vapors from effluents.
Other substances like silica gel and activated alumina are used as ad-
sorbents in some cases. 34
                               8

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Masking

Odor masking can be employed to cover up non-toxic pollutants.  In this
method a pleasant smelling or counteracting reagent is injected into the
odor-contaminated air.  The masking agent acts in one or more of the
following ways:  (1) overwhelms the odor, (2) modifies the properties of
the odorant to produce a less objectionable odor, or (3) numbs the sense
of smell momentarily so that the odor does not seem offensive.  Masking
agents are usually aromatic compounds like benzyl acetate and phenyl-
ethyl alcohol. The advantage of this method is its low capital investment.
Masking generally cannot be recommended where odor ants in large quanti-
ties are emitted.
       RESEARCH AND DEVELOPMENT OF ODOR CONTROL

As noted earlier in this paper, odor control problem definition and
quantification,  odor  measurement, and odor control  are largely unde-
veloped technologies.  Very little research and development to bridge the
gaps in this air pollution control area are underway.  Limited work is
being done to identify and deal with the problems of odor control from
motor vehicles; however, no analogous programs can be identified for
the equally or more  important problem of odor control from stationary
sources.

Some odor control research relating to kraft mill effluents has been going
on for more than 10  years under the sponsorship of the Public Health
Service6,37 ancj the  British Columbia Research Council. 38  TO a large
extent, research in this field has been oriented to a detailed study of the
reactions that contribute to odor pollution so that processes may be
changed to overcome this  problem.  The principal control methods de-
veloped'are incineration,  alkaline absorption (scrubbing), heat recovery,
black liquor oxidation, and chlorine treatment. The problem of krafc
mill odors has  not been completely solved; further research on basic
changes in both the pulping and recovery stages would aid in overcoming
the odor problem.

Research and development is urgently needed to control chemical and
rendering plant odors, since the methods now being employed are in-
adequate.   The large number of complaints received in surveys on odor
problems  attest to this need. ^

A well-supported research program extending over the next 5 to 10 years
will be required to develop technology for control of  odor pollution to a
level comparable to ihose for control of particulate and many gaseous
colluiants.

-------
         RECOMMENDATIONS FOR DPCE RESEARCH AND
               DEVELOPMENT ON ODOR CONTROL


A.  Simple odorous gases and vapors that are known to be present as
objectionable effluents from industries should be selected for control
research.  Examples of pure  compounds that have been identified in
complaints include

                      Acrylates        (
                      Acrolein        < Plastic industries

                      Acrylonitirile    (


                      Methyl mercaptan(.

                      Dimethyl sulfide  < Pulp mills, rendering plants
                      Dimethyl disulfide (^
                      1,5 diaminopentane (cadaverine) - Rendering
                                                         plants

The Manufacturing Chemists Association has very recently published
their latest findings on odor threshold research on 53 odorous com-
mercial compounds  (Appendix C).  This information should provide a
basis for evaluating odorant removal efficiency.

B.  Selected odorant compounds should be analyzed directly by instru-
mental methods.  A gas chromatographic analyzer appears to be most
suitable for accurately analyzing mixtures of odorant compounds over a
wide range of concentrations (pure compound to < 0.5 ppm).

C.  A screening study of scrubber reactants for controlling odorant
compounds should be conducted:

    1.   The effectiveness of various scubbing liquids or catalysts in
        removing odorants from gas streams should be determined in
        bench-scale screening tests.  Gas bubblers and liquid-gas re-
        action vessels should be employed.

    2.   Rates of reaction or absorption under variable  conditions of
        composition of scrubbing reagent, pH of the liquid, temperature,
        and inlet  gas concentration should be suited.
                               10

-------
    3.   Results of the screening test should be used in the selection of
         a scrubber system for further research.


D.  A preliminary pilot- or bench-scale odor control process design
should be developed. The economics of the process should be evaluated.

E.  Different types  of scrubbers should be evaluated for their efficiency
in separation of odorants from effluent streams.

    1.   The design features of the scrubber unit should be developed
         from studies of the effect of operating conditions on efficiency
         of odor control.

    2,   Scrubbers as gas-liquid chemical reactors should be evaluated
         on a pilot scale.

    3.   Economically advantageous related phenomena like  condensation
         should be incorporated  in scrubber designs.


F.  Fundamental principles and relationships that guide the improve-
ment  of scrubber systems as control devices should be  investigated.  For
example, combined adsorption of odorants.on solid particles and removal
in scrubbers may  lead to the development of systems that would remove
particulate and gaseous pollutants in a single unit.

A proposed work schedule for the above program is attached as
Appendix D.
                                11

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                          Table 1
             ST. LOUIS SURVEY: FREQUENCY
           OBJECTIONABILITY OF ODOR TYPES6
Odor Type
Chemical
Food
Combustion
General industrial
Animal
Combustion waste
Decomposition
Vegetation
Miscellaneous
No description
% Frequency
17.8
2.7
30.7
5.3
4.4
22.8
4.3
2.5
3.7
6.3
Averages
% Objectionability^
80.9
12.1
65.3
62.0
98.-0
50.6
83.2
8.7
51.7
60.7
% frequency = positive observations -rtotal positive observations, %.

% objectionability = unpleasant observations -i-positive observations, %.
                            12

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    Pollutant
Vanillin
Skatole
Musk, synthetic
Ethyl Scleno
     mercaptan
Ethyl mercaptan
Allyl mercaptan
Ethyl selenite
Propyl mercaptan
Allyl disulfide
Hydrogen sulfide
Ethyl sulfide
Butyric acid
Idodoform
Valeric acid
Methyl mercaptan
Apiolc
Chlorine
Pyridine
              Formula
CH3OCgH3(O?I)CHO-
CgH4-C(CH3)-CH-NH
C-CEL-CH,-CHQ-C
     o    <5    o
C0H,-SeH
 /  5
CH2-CH-CH -SH
C9H,-Se-C9H,
 2,  5     25
CH9-CH-
   £1
H.S
                     CH-
CH3-CH2'CH2'COOH
CHI3
(CHJ9-CH-CHo'COOH
   O &        £*
CH3O-CH2-CH-CH2CH3O-O-CH2'O
C19
  £j
C5H5'N'
         Odor

Sweet, aromatic
Fecal
Musk
Foul, foetid

Decayed cabbage
Garlic
Putrid, nauseating
Unpleasant
Garlic
Rotten eggs
Foul, garlic
Rancid, perspiration
Antis eptic
Unclean body odor
Decayed cabbage
Parsley
Pungent
Empyreumatic
Odor Threshold,
     ppm
                                                                    32.10'
                                                                    75
                                                                    42.10
                                                                    18.10
                                                                                              _Q
         -8
         -7
    16.10
      5.10
    62.10
    75
      1.10
    11
    25.10
    28
    37
    62
    11.10
    63
      1.10
    12.10
                                                                         -6
                                                                         -5
                                                                         -6
                                                                         -5
                                                                         -4
                                                                         -2
                                                                         -3

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                                         Table 2. Cont'd
    Pollutant
              Formula
        Odor
                                                                                  Odor Threshold,
Dimethyl sulfide
Diacetyl
Ammonia
Ozone
Hydrogen selenide
Phenol
Dimethylamine
Carbondisulfide
Acrolein
Camphor
Sulfur dioxide
Trimethylamine
Trichloroethylene
CH3-CO-CO-CJI3
°3
H-SeH
    p-
 6  5
CH -
   o
cs
CH2'CH-CHO
S0
(CH3)3N
CH-C1-C-C1,
Decayed cabbage
Sweet butter
Pungent
Irritating
Putrid
Empyseumatic
Fishy
Rotten
Hot fats
Aromatic
Pungent
Fishy-ammoniacal
Aromatic
  2.10
 25.10
 37
  1.10
  3
  3
  6
  7.7
 15
 16
 30
  4
250
                                                                       -2
                                                                       -3
                                                                       -1

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                     APPENDIX A
RESULTS OF AN OPINION SURVEY CONDUCTED IN 19555

        Source                      ^Frequency, %
   Chemicals                              62
   Vehicles                                52
   Paint and Varnish                       49
   Food Processing                        47
   Domestic (homes, etc.)                  45
   Rendering Plants                        43
   Plastics                                33
   Oil Refineries                           31
   Coke Works                             31
   Rubber                                 27
   Steel                                   25
   Insulation                               21
   Fish                                   21
   Gas Works                              19
   Pharmaceutical                         19
   Soaps and detergents                     17
   Breweries                              15
  a/           _ no. of times the source was mentioned
    Frequency  -        total nQ> Qf questi0nnaries
                          15

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                            APPENDIX B

            SOURCES OF ODORS AND THEIR COMPOSITION
               Source

Chemical manufacturers:
    Organic chemicals byproduct,
    electrolysis

    Dye-making, explosives, lacquers,
    refrigeration, textiles, chemicals

    Soal making, fats, oils, glycerine,
    thermal decomposition, food
    processing

    Resins, adhesives, rubber,
    paints, varnish coatings

    Petroleum, petrochemicals
Pulp and paper manufacture
Fertilizers,  fish wastes, spent acids
Food products, canning
Rendering, tanneries
Pharmaceuticals, breweries,
fermentation

Municipalities, dumps,  lagoons,
settling ponds

Textiles, paper
          Composition
Chlorine
Ammonia, hydrogen cyanide
Aldehydes, dimethyl amine
Phenolics, sulfur compounds,
formaldehyde, solvents

Hydrogen sulfide, organic sulfur
compounds, hydrocarbons

Hydrogen sulfide, organic sulfur
compounds

Amines, mercaptans, reduced
sulfur compounds

Decomposition products of nitro-
genous compounds

Amines, reduced sulfur compounds,
caproic acids, ammonia

Amines, reduced sulfur compounds
Decomposition products of nitro-
geneous compounds

Urea, starch decomposition products
                                  16

-------
                       APPENDIX B Cont'd
             Source

Coal gas manufacture



Natural gas

Diesel exhaust

Coffee and chicory roasting



Domestic incinerators
          Composition
Sulfur compounds (hydrogen suliide,
carbon disulfide , thiophene, thiols,
carbon oxysulfide)

Hydrogen

Aldehydes

Aldehydes , hydrogen sulfide, mer-
captans,  phenols, organic acids,
hydrocarbons

Organic acids ;  aldehydes , hydro-
carbons , nitrogen oxides, ammonia
                                17

-------
                       APPENDIX C
             Table 1.
       CHEMICAL
Acetaldehyde
Acetic acid
Acetone
Acrolein
Acrylonitrile
Allyl chloride
Amine,  dimethyl
Amine,  monomethyl
Amine,  trimethyl
Ammonia
Aniline
ODOR THRESHOLDS IN AIR
 (ppm by volume)

                   RESPONSE
                                                     100%
Benzene
Benzyl chloride
Benzyl sulfide
Bromine
Butyric acid
             2.14
             0.01
             0.0021
             0.047
             0.00047
  4.68
  0.047
  0.0021
  0.047
  0.001
Carbon disulfide
Carbon tetrachloride
  (chlorination of CSj
Carbon tetrachloride
  (chlorination of CHj
Chloral             4
Chlorine
p-Cresol
             0.1

             10.0

             46.8
             0.047
             0.314
             0.00047
  0.21

 21.4

100.0
  0.047
  0.314
  0.001
Dimethylacetamide
Dimethylformamide
Dimethyl sulfide
Diphenyl ether
  (perfume grade)
Diphenyl sulfide
            21.4
            21.4
             0.001

             0.1
             0.0021
 46.8
100.0
  0.001

  0.1
  0.0047
                             18

-------
                         Table 1.  Cont'd
           CHEMICAL
Ethanol (synthetic)
Ethyl acrylate
Ethyl mercaptan

Formaldehyde

Hydrochloric acid gas
Hydrogen sulfide (from Na?S)
Hydrogen sulfide gas
        RESPONSE
  4.68
  0.0001
  0.00047

  1.0

 10.0
  0.001
  0.00021
 100% •
10.0
 0.00047
 0.001

 1.0

10.0
 0.0047
 0.00047
 Methanol
 Methyl chloride
 Methylene chloride
 Methyl ethyl ketone
 Methyl isobutyl ketone
 Methyl mercaptan
 Methyl methacrylate
 Monochlorobenzene

 Nitrobenzene

 Perchloroethylene
 Phenol
 Phosgene
 Phosphine
 Pyridine

Styrene (inhibited)
Styrene (uninhibited)
Sulfur dichloride
Sulfur dioxide

Toluene (from coke)
Toluene (from petroleum)
Tolylene diisocyanate
Trichioroethylene

p-Xylene
100.0            100.0
     [Above 10 ppm]
214.0            214.0
  4.68            10.0
  0.47             0.47
  0.001            0.0021
  0.21             0.21
  0.21             0.21
  0.0047

  4.68
  0.021
  0.47
  0.021
  0.01

  0.047
  0.047
  0.001
  0.47

  2.14
  2.14
  0.21
 21.4

  0.47
 0.0047

 4.68
 0.047
 1.0
 0.021
 0.021

 0.1
 0.047
 0.001
 0.47

 4.68
 2.14
 2.14
21.4

 0.47
                                 19

-------
                           REFERENCES


 1.  Duffee, R.A.  J. Air Pollution Control Assoc. 18, pp. 472-474. 1968.

 2.  Lund, H. F.  Factory.  October,  1965.

 3.  Brewer, G. L.  Odor control for kettle cooking.  1962.

 4.  Summer, W.  Methods  of air deodorization.  New York, Elseiver.
     1963.

 5.  Bergen, J.J.  Chemical Engineering, pp. 23,9-250.  August, 1957.

 6.  Kenline, P. A.  In quest of clean air for Berlin, New Hampshire.
     US   DHEW, PHS, Div.  Air Pollution,  Tech. Rept.  A62-9, 1982.

 7.  Turk, A.  Heating, Piping and Air Conditioning, p. 207. January,
     1968.

 8.  Duprey, R. L.  Compilation of air pollutant emission factors.   US
     DHEW, PHS. Natl. Center for Air Pollution Control, Publ. No. 999-
     AP-42, 1968.

 9.  City of Cincinnati, Intercommunity Air Pollution Control Program,
     Activities for 1966 and  1967.

10.  Wright, R. H.  Paper presented at the 55th Annual Meeting of APCA,
     Chicago,. Illinois, May 20-24, 1962.

11.  Studies to assess the social and economic impact of odors.  Request
     for Proposal,  PH 22-68- Neg. 7.

12.  Crocker, E.G. , and Henderson, L.F.  Amer. Perfumer. 50, p. 164,
     1947.

13.  Byrd, J. F. , Mills, H.A. , Schellhase, C.H. , and Stokes,  H.E.  J.
     Air Pollution Control Assoc. 14,  pp.509-516.  1964.

14.  Byrd, J. F.  J. Air Pollution Control Assoc. 7, pp. 58-59. 1957.

15.  Gex, N. F. , and Fox, F.A.  J.  Air Pollution Control Assoc. 7,
     pp.  60-61. 1957.
                                22

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16.   Prince, R.G.H. ,  andlnce, J, H. J. Appl. Chem.  8, pp.314-321.
     1958.

17.  Byrd, J. F. , and Phelps, A. H. , Jr. In: Air pollution. Vol. 2.
     Analysis,  monitoring, and surveying.  Ed. byA.C. Stern. 2nd ed.
     New York, Academic, pp. 305-327, 1968.

18.   Mills,  J.L. , Walsh, R.T. , Luedtke, K.D. , and Smith,  L.K. J.
     Air Pollution Control Assoc. 13, pp. 467-475.  1963.

19.  Cederlof,  R. ,  Edfors, M. L. , Friberg, L. , and Lindvall, T.
     TAPPI, 48, p. 405. 1965.

20.  Springer,  K. J. An investigation of diesel powered vehicle  odor
     and smoke, Part II.  National Air Pollution Control Adm.  Final
     Report, Contract No. PH 86-67-72. February,  1968.

21.   Sullivan, D. C. , Adams, D. F. ,  and Young, F.A.  Atmospheric
     Environment. 2, pp. 121-133.  1958.

22.  Standard method for measurement of odor in atmospheres (dilution
     method).  ASTM Designation D-1391-57, ASTM, Philadelphia.
     pp. 185-188, 1959.

23.  Duffee, R.A. , Schultz, E.G. , and Ray, H.W.  Development of an
     odor measurement technique for domestic gas incinerators.  Pro-
     ject DAG-4-M, Catalog No. 140/DR, New York, Amer.  Gas Assoc.
     1961.

24.  Grune, W. N.  Chueh, C.-F. , and Hawkins, J.M.  J. Water Pollution
     Control Federation, 32, pp. 942-948. 1960.
                           i
25.  Jerman, R.I. , and Carpenter, L.R. J. Gas  Chromatography.  6(5):
     298-301. 1968.

26.   Schneider,  R.A. ,  Costiloe, J.R. , Vega, A. , and Wolf,  S.  J. Applied
     Physiol. 18, pp. 414-417. 1963.

27.   Ettre,  L.S.  J. Air Pollution Control Assoc.  11, pp. 34-42. 1961.

28.   Adams, D.F. , and Koppe, R.K.  TAPPI. 42, pp. 601-605. 1959.

29.   May, J. Staub (English). 25(4):19-23.  1965.

30.   Dravnieks, A., and Kroloszynski, B. F.  J.  Gas Chromatography. 5,
     pp.  144-149. 1968.

                                23

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 31.  Wright, R.H.  TAPPI. 35, pp. 276-280. 1952.

 32.  Douglass, I.E.  J. Air Pollution Control Assoc.  18,  pp.  541-544.
     1968.

 33.  Possett,  H.S. , and Reidies, A. H.  I&EC, Product Res. & Dev.
     4, pp.  48-50,, 1965.

 34.  American Soc. Heating,  Refrigerating, Air-Cond. Engineers.
     Tech. Com. 1.6.   ASHRAE Handbook of Fundamentals,  ch. 12,
     pp. 173-178. 1968.

 35.  Walsh, R.T.  J.  Air Pollution Control Assoc. 17, pp. 94-97.
     1B67.

 36.. Borger, H. F.  The solution of a major odor problem. Clean Air
     Week Conf. , Cincinnati,  Ohio. October, 1963.

37.  Shulman, H. US  DHEW,  PHS, Natl. Air Pollution'Control Adm. ,
     Grant No. AP 00246-04.   (Project title: Kinetics of Adsorption by
     Molecular Sieves.)  Clarkson College of Technol. , Potsdam, N.Y.
     1967.

     Calvert, S.  US DHEW, PHS, Natl.   Air Pollution Control Adm. ,
     Grant No. AP 00320-04.   (Project title: Basic Study  of Air Pol-
     lution Control Wet Scrubbers.) Pennsylvania State Univ., University
     Park, Pa.  1967.

     Vaska, L.  US DHEW, PHS, Natl. Air Pollution  Control Admin. ,
   _, Grant No. AP 00574-01.   (Project title: Reversible" Metal Com-
     plexes with Air Pollutants.) Clarkson College of Technol., Potsdam,
     N.Y.  1967.

     Hendrickson, E.R.  US DHEW, PHS, Natl. Air Pollution  Control
     Adm. ,  Grant No. AP 00256-05.  (Project title:  Manual of Methods
     for Ambient Air Sampling and Analysis.) American Public Health
     Assoc.  , New York, N.Y.  1967.

38.  Adams, D.F.  TAPPI. 48(5):83A-87A.  1965.
                                24

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             APPENDIX B
             WORK PLAN
Odor Pveinoval from Air by Adsorption
            on Charcoal
       Contract No,  EHSD 71-4
            Submitted by
Benjamin G. Kyle
Professor of Chemical
Engineering
                                     N.  Dean Eckhoff
                                     Assistant Professor of
                                     Nuclear Engineering
        Kansas State University
        Manhattan,  Kansas 66502
            September 1970

-------
                         WORK PLAN






In delineating the work plan for this contract research several distinct




tasks can be identified.  These tasks are described below and are




scheduled on the accompanying "Milestone Chart."







1.  Construction of Experimental Apparatus.  A volumetric type of




adsorption system will be constructed which utilizes radioactive tracers




for measurement of  the extremely low concentration of odorous compounds




in the gas phase.  The gas  containing the tagged odorous compound will be




circulated  through a  shallow bed of charcoal while the concentration of




the tagged  compound in the  gas phase is continuously monitored with a




radiation detector.   A material balance calculation gives the adsorbent




loading  corresponding to any adsorbate partial pressure.  Because the




output of the  radiation detector is continuous, both kinetic and equil-




ibrium data may be obtained.







Initially a gas flow  cell filled with powdered anthracene crystals




will be  used in conjunction with a Model 3375 Packard TRI-CARB Scintil-




lation Spectrometer,  A portion of the tagged (with   C,   S, or  H) gas




being tested will flow throagh the cell.  The anthracene crystals will




serve to detect the beta particles resulting from the decay of the




radioactive isotope disintegration.  The signal from the anthracene crystal




scintillator is analysed by a pulse height analyzer and the result is




stored in one or more memory units.  The Model 3375 TRI-CARB system




consists, basically,  of three single channel analyzers which have the




capability of varying the lower level discriminator as well as the window

-------
width for each channel.  This variability allows one to discern between

three different beta particles emitting radio-isotopes, provided their

maximum energies are well separated.  For example, it is quite easy to

discern  H from   C, but not as easy to discern   C from   S.  However,

it should be possible to tag three compounds with  H,   C, and   S and

to determine the relative concentration of each compound which flows

through the cell.


If the flow cell scintillation detector yields unusable data, a thin

window barrier Si semiconductor detector will be inserted in place of it.

These dectectors are not as efficient as the flow cell scintillation

detector nor can different isotopes be discerned, but they are compact,

rugged, inexpensive, and can be used as a beta particle detector.


Finally if neither of these systems work we will have to purchase the

Johnson Laboratory TRITON flow ionization chamber as listed in the

proposal.  A copy of the specifications of this detector is attached.


2.  Literature Search.   A literature survey will be donducted covering

the following topics:

     Equilibrium and kinetic data for the adsorption of odors on charcoal.

     General gas phase adsorption equilibrium — theoretical treatment and
     engineering correlations.

     General gas adsorption kinetics — theoretical treatment and
     engineering correlations.


3.  Testing and Evaluating the Experimental Apparatus.  The apparatus

will be tested by determining the adsorption equilibrium data for Ethyl

Mercaptan (tagged with Carbon 14) on Pittsburgh BPL activated carbon.

-------
These data can be  compared with  those of Grant, Manes, and Smith  (1) who




report  the adsorption isotherm for  this system in the range 10    to 10




atmospheres.
4   Experimental  Study -- Adsorption of Specific Odorous Compounds.  When




the experimental  apparatus  and  technique have been perfected, adsorption




equilibrium  and kinetic  data will be obtained for certain selected compounds




The specific compounds chosen for study will be selected on the basis of




their  importance  as  air  pollutants  (e.g. mercaptans, disulfides5 and




aldehydes).   To better understand the adsorption equilibrium behavior




of odorous compounds  it  will be necessary to study several compounds




within a homologous  series.  Adsorption equilibrium data for mercaptans




on charcoal  have  been reported  (1)  for the moderate to low pressure




range  and  a  study of  these  systems  should indicate whether adsorption




equilibrium  data  at  ultra low pressure can be obtained from data at




moderate pressures.







5.  Correlation of Adsorption Equilibrium Data.  Concurrent with the




experimental study work  will be directed toward obtaining an under-




standing of  the theromodynamics of  adsorption at low concentrations, and




developing correlations  for the adsorption phase equilibrium data




required for  design  of systems for  adsorption of odorous compounds.  The




work of Grants Manes, and Smith (1) implies that adsorption forces depend




mainly on the nature  of  the functional groups comprising the adsorbate




molecule and  suggests that separate adsorption equilibrium correlation




curves may be expected for each homologous series.  Such a development




would allow  the prediction/of adsorption equilibrium data for any member

-------
of a homologous series once these data have been determined experimentally




for one member of the series.   This approach might be extended to adsor-




bates with several types of functional groups by means of a "group con-




tribution" approach similar to that employed by Pierotti et al.  (2) for




correlating liquid phase solution behavior.   It is also possible that




the corresponding states principle (3), which has proved useful  in dealing




with gas phase interactions, would allow the correlation of adorption




equilibrium data if the significant molecular parameters can be  identified.






6.  Modeling of Experimental Kinetic Data.   The experimental kinetic




data will be analysed using both the differential and integral approaches.




With the differential approach one determines the instantaneous  rate of




adsorption at various times from the quantity adsorbed versus time data




and uses this to test rate expressions arising from various proposed




mechanisms.  The appropriate mechanism is established from the condition




that for a single run parameters determined from the instantaneous rate




of adsorption evaluated at different times  should be identical.   In




addition to this, these parameters should be physically realistic.  The




integral approach is based on  integrating these various rate expressions




and comparing the resulting quantity adsorbed - time relationships with the




experimentally determined relationship.  If an integrated rate expression




can be fitted to the experimental data and the evaluated parameters appear




realistic, that mechanism is said to be valid.  Both the differential




and integral approaches will be considered in analyzing the kinetic data.




The differential approach has  the advantage of being capable of  testing




any postulated mechanism, while the integral approach is restricted to




those simpler mechanisms whose rate expressions are integrable.

-------
The object of the modeling study is to establish the rate mechanism

and to determine the dependence of the parameters in the rate expression

upon the system variables so that design of adsorption systems for odor

removal can be accomplished.


                         References

1.  Grant, R. J, , Manes, M. , and Smith, S. 3., A.I.Ch.E.J. , j>s 403(1962),

2,  Pierotti, G. J. „ Deal, C, H., and Derrs E. L., Ind. Eng. Chem., 51,
    95 (1959).

3.  Prausnitz, J. M. 5 "Molecular Thermodynamics of Fluid-Phase Equilibria,
    Chapter 4S Prentice-Hall, Englewood Cliffs, N. J. 1969.

-------
                                                      i   I   U
                     H3
                                   v^yr^'tsms      (      Acci-jj^iortos
                            Low Leve! Detection   ••    (VIccGMrement
                                        for Radioactive Gsces
                           C14  /  A41   r  Rn222   (   S35   c   Kr05  r
  C	
                                       Sensitivity: H3:   10 |j.Ci/M3 F.S.  °
                                       Accuracy  ± IOX  c
                                       Sensitivity. Gamma: 50^R/hour F.S.  •
                                       Input Filter: 0.5 I'nicron    Electrostatic Precipiiator °
-•••-ll--- -*'*   '''••- J •"
              ^~-*Ht*^y
                                             iia Compensation:  to 5 mR/liour •
                                         Flo\v Chambers: 10 liter volume  •  Cleanable  o
                                         Po:;i'.ive Displaccnicnt Air Pump: 1 to 10 liters/mil. <>
                                         Alarm:  N'ariablc Set Point '  Visual ••  Aural  «
                                         Closed and Open Loop Operation  :  Gas Tigiit  *
                                         Recorder Output   Remote Accessory Connector o  « "

                                                             TRITON r.'odel 755C
       similar to 935B except:

       Sensitivity.  II3:  100 (,LCi/M3 F.S.  •
       Sensitivity.  Gamma:  0.5 mR/hour F.S.  o
       Flow Chanib''1)-:  1.2 liter volume  «-
       Flow Rate:  9 liters/ruin.  »
                                                     ir,n"---
                                                           '.cTcC^-1*
             TRITON l-'Gciel  10-55B
                         -~™^^^
                                            similar to 755C except:
                                            Sensitivity.  H3:  50 (iCi/M3 F.S.  •
                                            Sensitivity.  Gamma:  0.25 mR/hour F.S.  «
                                            Portable '   Rechargeable Ni-Cad Batteries  °
                                            Flow Rate:  2 liters/min.  •
                                                                       TRITOW CALIBRATOR  Morfel  CM
!iO:^  nZ,V;OTE ALArJ.1  Model RA-1
     '  Visual and Aural Alarm
irercd frojn main instrument •
•cwtcs to 500 feet or more
ion main instrument  c '
                                                               Accurately Assayed   ,f..,	.^^
                                                                 Radioactive Gas e   [,   .-.-:
                                                               Convenient:          ^•'."T'vF'l
                                                                 Self-Containcd  t    ^' ^_';. ~
                                                                 Portable o        /'?   ^
                                                               Rapid Calibration:     '^s--*^
                                                                 3 to 5 minutes «
                                                               Low User Cost: 1000 or  more calibrations  '•
                                                               No Special AEC License  Required  «
    A	              For wore information, caU or write.  Ash far file TM.

^S2717  TT-V    T                           T
    '	1 )  I   . '  f\ T..T TVT C! T' f^ T-tT   ;    •  A  TV f\ T>  A  O^ /^ T

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    Contract:  Odor Removal from Air by Adsorption
                on Charcoal

    Contractor:  Kansas State University
                 Manhattan, Kansas

          Milestones
 Ml  Construction of Experimental
      Apparatus

 M2  Testing  the Experimental
      Apparatus

 M3  Experimental Study

 M4  Literature Survey _

 M5  Correlation of Adsorption
      Equilibrium Data

 M6  Modeling of Experimental
      Kinetic Data

 M7  Preparation of Final
      Report
                                                 Contract No.
                                                 EHSD 71-4
                                    Contract Dates            Project(Officer
                                   8/27/70 - 8/27/72        Dr.  Belur N.  Murthy
                                                                    Time
                                                 J   Actual
                                           22223   Estimated
                                         f//
                                            1370
                                                                1172.
                                                                           435-  .
                                                                                  rt
                                                                             3o
                                                                             Z5-
                                                                                 •3
                                                                                 4J
                                                                                                          ti
                                                                                                          CJ
                                                                                                          w
                                                                                                          0)
                                                                                                          •H
                                                                                 o
C'j..--< Ir-.tion Dntc
 Actual
Kr, (. l.nuitrd
A A
2. 4
                                                                   MILKfiTONK CHART
~A /\ A
 3    7

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