United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Research Triangle Park NC 27711
EPA-600/2-79-199
November 1979
Research and Development
EPA/IERL-RTP
Procedures Manual:
Level 2 Sampling and
Analysis of Selected
Reduced Inorganic
Compounds
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency and
approved for publication. Approval does not signify that the contents necessarily
reflect the views and policy of the Agency, nor does mention of trade names or
commercial products constitute endorsement or recommendation for use
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
-------
EPA-600/2-79-199
November 1979
EPA/IERL-RTP Procedures Manual:
Level 2 Sampling and Analysis of Selected
Reduced Inorganic Compounds
by
R.G. Beimer, H.E. Green, and J.R. Denson
TRW Defense and Space Systems Group
One Space Park
Redondo Beach, California 90278
Contract No. 68-02-2165
Task No. 103
Program Element No. INE624
EPA Project Officer: Frank E. Briden
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
-------
TABLE OF CONTENTS
Page
LIST OF FIGURES ....................... 1v
LIST OF TABLES .......................
ACKNOWLEDGEMENT ....................... vlll
ABSTRACT .......................... 1x
1. INTRODUCTION ........................ 1
2. STREAM PARAMETERS FOR PROCESSES WITH REDUCED STREAMS .... 3
2.1 Sampling Stream Parameters .............. 3
2.2.1 Steel Plants .................. 4
2.2.2 Coke Ovens ................. .. . 8
2.2.3 Coal -Fired Boilers ............... 8
2.2.4 Refinery Operations .............. 13
2,2.5 Coal Conversion ................ 13
2.2.6 Fertilizer Manufacturing ............ 16
2.2.7 Forest Products ................ 23
2.2.8 Primary Nonferrous Metals ........... 23
3. SAMPLING TECHNIQUES FOR REDUCED INORGANIC SPECIES ....'.. 37
3.1 Solid: Integrated Composite .............. 38
3.2 Liquid: Integrated Composite ............. 38
3.3 Gas: Fugitive Emissions ................ 39
3.4 Gas: Time Integrated ................. 41
3.5 Gas: SASS Train .................... 41
3.5.1 SASS Distribution of The Hydrides; PHV AsH-.
and SbH, ......... ..... . . . . . . 42
3.5.2 SASS Distribution of Reduced Sulfur Species . . 46
3.5.3 SASS Distribution of Reduced Nitrogen Species
(NH3, HCN, and (CN).J ...... ...... . 50
continued...
11
-------
TABLE OF CONTENTS (continued)
Page
3.5.4 SASS Train Distribution for Mercury,
Selenium and Metal Carbonyls . . . . ...... 54
4. SAMPLING AND ANALYSIS OF GASEOUS REDUCED INORGANIC COMPOUNDS. 57
4.1 Sampling and Analysis of Acidic Reduced Inorganic
Gases ......................... 57
4.1.1 Sampling Techniques for Acidic Reduced
Inorganic Gases ................ 58
4.1.2 Analysis Methods for Acidic Reduced
Inorganic Gases ................ 62
4.2 Sampling and Analysis of Basic Reduced Inorganic Gases. 73
4.2.1 Sampling For Basic Reduced Inorganic Gases ... 73
4.2.2 Analysis of Impinger Solutions for Basic
Reduced Inorganic Gases ........ .... 75
4.3 Sampling and Analysis of "Neutral" Reduced Inorganic
Gases ............. ... ......... 81
4.3.1 Sampling and Analysis of Selected Metal
Hydrides (PH3, AsH3> and SbH) 81
4.3.2 Sampling and Analysis of The Volatile
Elements (Hg and Se) 100
4.3.3 Sampling and Analysis of Miscellaneous
Reduced Inorganic Gases 109
5. SUGGESTIONS FOR FURTHER RESEARCH 116
REFERENCES 118
111
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LIST OF FIGURES
Figure No. Page
2-1A Blast Furnace and Sintering Machine With
Associated Dust Collection System 9
2-1B Blast Furnace and Sintering Machine With
Associated Dust Collection System 10
2-2A Coke Oven Battery 11
2-2B Coke Oven Battery 12
2-3A Processing Plant for Typical Complete Refinery ....... 14
2-3B Processing Plant for Typical Complete Refinery 15
2-4A Simplified Gasification Complex (LurgO 17
2-4B Simplified Gasification Complex (Lurgl) 18
2-5A Simplified Liquifaction Complex (SRC) 19
2-5B Simplified Liqulfaction Complex (SRC) 20
2-6A Flow Diagram of The Process for Manufacture of
Ammonium Nitrate 21
2-6B Flow Diagram of The Process for Manufacture of
Ammonium Nitrate 22
2-7A Simplified Kraft Mill Flow Diagram 24
2-7B Simplified Kraft Mill Flow Diagram 25
2-8A Copper Smelting - Simplified Flow Diagram 28
2-8B Copper Smelting - Simplified Flow Diagram 29
2-9A Typical Flowsheet of Pyrometallurgical
Lead Smelting 30
2-9B Typical Flowsheet of Pyrometallurgical
Lead Smelting 31
2-10A Zinc Smelting Flow Diagram 32
2-10B Zinc Smelting Flow Diagram 33
2-11A Aluminum Cell (Prebaked Anode Type) 34
2-11B Aluminum Cell (Prebaked Anode Type) 35
continued
1v
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LIST OF FIGURES (continued)
Figure No. Page
3-1 Probes for Continuous Liquid Sampling 39
3-2 Probable Distribution of PH.,, AsH, and SbH~
In The SASS Train J. ....... 43
3-3 Probable SASS Distribution of Reduced
Sulfur Species ..... 47
3-4 Probable SASS Distribution for Reduced
Nitrogen Species 51
3-5 Probable SASS Distribution for Hg, Se, and
Metal Carbonyls 55
4-1 Sample Preparation Apparatus for Evaluation
of Implnger Solutions 60
4-2 Typical Grab Gas Sampling System 63
4-3 Regeneration Apparatus for Samples Obtained
Using Implnger Sampling Techniques 65
4-4 Typical Chromatogram for Reduced Inorganic
Gases Using Porapak QS 68
4-5 Resin Adsorption Trap for Preconcentratlon
of Solid Adsorbed or Grab Samples 70
4-6 Ammonia Distillation Collector for Implnger
Trapped Samples 76
4-7 Reduction Chemistry of Arsenic Adds 83
4-8 Reduced Gas Evolution Apparatus 87
4-9 Resconstructed Gas Chromatogram of The
Hydrides Produced by Reduction Procedure 89
4-10 Mass Chromatograms for Oxygen (M/es32)
and Phosphlne (M/e=34) Showing Coelutlon . 90
4-11 Mass Spectrum of Phosphlne and A1r (Scan 22) 91
4-12 Mass Spectrum of Stlblne (Scan 325) 92
4-13 Mass Spectrum of Arslne (Scan 128) 93
4-14 Mass Spectrum of Methyl Arslne (Scan 454) 94
continued
-------
LIST OF FIGURES (continues)
Figure No. Page
4-15 Arsine Calibration Curve 96
4-16 Stibine Calibration Curve 97
4-17 Schematic of Paraho Retort 99
4-18 The Function of Selective Absorbers for
The Sampling of Gaseous Mercury Compounds 102
4-19 All Glass Sampling Apparatus for Selenium 110
4-20 Impinger Sampling System for COS and CS2 112
vi
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LIST OF TABLES
Table No. Pfl9e
2-1 Industries and Processes Producing 5
Reduced Inorganic Species
•3C
2-2 Selected References for Process Information
4-1 Implnger Trapping Efficiency
4-2 Recovery of Acid Gases from Implnger Solution
79
4-3 Summary of Gas Chromatography Procedures for HCN Ie-
4-4 Effectiveness of Columns for Amlne Analysis 78
4-5 Ammonia Analysis Results from Paraho Shale Oil Facility . . 80
4-6 Field Test Results for Arslne • • 10°
4-7 Preparation of S11Iconized Chromosorb W
(HC1) For Mercury Sampling 104
4-8 Preparation of NaOH Treated Chromosorb W
For Mercury Sampling 105
4-9 Preparation of Silvered Glass Beads
For Mercury Sampling 106
4-10 Preparation of Gold Coated Glass Beads
For Mercury Sampling 107
4-11 Field Verification Results of Samples Taken at
The Paraho 011 Shale Demonstration Facility 114
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ACKNOWLEDGEMENT
This report has been submitted in partial fulfillment of the
requirements on EPA Contract No. 68-02-2165, Technical Directive Number 8.
The authors wish to acknowledge the initial support and insight of Dr. Robert
Statnick, currently assigned to EPA, OEMI, the project officer for the
early phase of this work. His ideas and suggestions are an integral part
of this task report. In addition the support and encouragement of Frank
Briden, Project Officer and James Dorsey, Branch Chief PMB, IERL» is
acknowledged.
viii
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SECTION 1.0
INTRODUCTION
/
In the past few years Intrest has grown in the determination of
specific Inorganic compounds being emitted from Industrial sources rather
than the general determination of total metal emissions. The identification
of specific compounds is necessary to throughly assess the environmental
impact of a given source. Health effects are generally based on specific
compounds not on compound classes which are determined in industrial
effluents routinely. The purpose of this study was to develop sampling
and analysis techniques for the determination of emission rates of specific
reduced inorganic compounds from stationary sources. The report includes a
review, of the current literature on sampling and analysis together with
methods evaluation in laboratory and field for the sampling and analysis
techniques proposed.
For the purpose of this study reduced inorganic compounds are defined
as any metal or non-metal which is bound to hydrogen,1n its zero oxidation
state,or 1s bound to carbon. A group of industrial categories has been
reviewed as to possible emissions of reduced inorganic compounds. Several
of the typical effluent streams from these various industrial categories
have been identified as candidate sources of reduced inorganic compound
emissions based on the chemistry and literature Information on the
processes. Generalized sampling points have been Identified for typical
plant operations.
The overall goal of this task was to establish sampling and analysis
techniques which can provide for an accuracy of -25% in the determination
of specific reduced inorganic compounds from various industrial sources.
A detailed evaluation of the Source Assessment Sampling System (SASS) as
a sampling device for reduced inorganic compounds at the trace level was
1
-------
made and is reported tn detail. The results of this evaluation, show the
SASS train to be inadequate for sampling and subsequent compound identifica-
tion of the more reactive reduced inorganic compounds. Many of the species
of interest are lost in various parts of the sampling train, or their
structure modified in such a way that direct determination of the original
emission form cannot be made.
In field sampling applications, analysis of the samples must be
conducted remote from the sampling site. Analytical instrumentation which
can provide compound identification, especially on highly reactive species,
is generally not available at remote locations. Therefore, stability,
storage and transport are serious considerations in proposing a sampling
and analysis technique. Certain assumptions must be made about many of the
streams to be sampled, and the evaluation of potential interferences from a
wide variety of sources has not been exhaustively examined. A significantly
larger data base is required before the methods proposed in this report can
be routinely applied to a wide variety of sources. A thorough examination
of possible interferences is also required especially in those instances
where mixed reduced and oxidizing streams are encountered.
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SECTION 2.0
STREAM PARAMETERS FOR PROCESSES WITH REDUCING STREAMS
The specification of appropriate sampling procedures for any specific
chemical requires an understanding of its physical and chemical properties
as well as the physical and chemical parameters of the stream in which it
may be found. This section provides the required information about process
and effluent streams which may contain reduced inorganic compounds by
identifying:
1) those industries which may be sources of reduced inorganic
species;
2) the specific effluent streams which may contain the species
in question and
3) methods which can be used to sample the identified streams.
The data concerning industrial sources of reduced inorganic compounds
were gathered from the literature whenever possible. The published
information was supplemented by analysis of the chemistry and operating
parameters of the individual processes and personal contact with knowledgable
individuals.
The results of the effort to identify the pertinent industries and
effluent streams are described in this section and information concerning
sampling methods may be found in Section 3.0.
2.1 SAMPLING STREAM PARAMETERS
For the purpose of this investigation, a reduced inorganic compound
has been defined as any metal or non-metal which is bound to hydrogen,
is in the zero oxidation state, or is bound to carbon. Unfortunately,
the literature contains very few references which identify specific
reduced compounds in effluents from industrial processes. Generally, the
species cited are relatively common well known compounds such as HpS, COS,
3
-------
NH3 and simple cyanides. Therefore, the literature search was supplemented
by an examination of the chemistry and operating conditions of a number of
processes which may have the potential to form reduced compounds not
commonly considered in source assessment efforts. The following process
parameters were selected as likely to be condusive to the formation of
reduced species:
• Operations in which hydrogen is present in significant quantity.
t Operations which are oxygen deficient.
• Processes which contain metal oxides in a partially reduced
state. Such oxides may interact with various agents to form
reduced species. For example, the thermodynamically stable
oxidation states of MnO, ZnO, CaO, and V203 can react with HgS,
within the temperature range of 300°C to 800°C, to form their
respective reduced metal sulfides as follows:
MnO + H2S -»• MnS + HgO
ZnO + H2S ->• ZnS + H20
CaO + H2S -> CaS + HgO
V2°3 + 3H2S * V2S3 * 3H2°
• Processes which generate substantial quantities of carbon
monoxide or nitrogen oxide in the presence of those elements
capable of forming carbonyls or nitrosyls.
As a result of the application of these criteria and the literature
survey, sixteen processes employed in at least seven industries were
identified as potential sources of effluents containing reduced inorganic
species. The identified industries are discussed in the following sections
and summarized in Table 2-1. The table highlights characteristics of the
effluents from the process operations of interest. Following Table 2-1-
flow diagrams are presented for eleven of the most important process types
along with potential sampling points.
2.2.1 Steel Plants
Hydrogen and hydrogen sulfide have been cited in the literature as
4
-------
en
Table 2-1
Industries and Processes Producing Reduced Inorganic Species
Process Idenficatlon
1) Steel Plant
@ Blast Furnace
® Sinter Plant
® Windbox:
© Discharge
end:
© Coke Ovens
Q) Oven off
gas
© Quench
Tower
(3) Sour
Quench
Water
2) Coal Fired Boilers
Effluent Characteristics from Predominant Process Operations
Particulate Data
Size
Distribution
15-90* < 74u
15-45* < 40 u
9-30* < 20 u
4-19* < I0\s
1-10* < 5u
80* < 100
10* < 10
Highly
Variable
95-97* > 47n
Not
Applicable
25* < 10
49* < 20
m< dd
V "ft
gr/SCF
4-30,
7-10 avg.
0.2-3.2
1-5
.
1-15
0.05-0.1
2.9 to
3.7 avg.
Flow Rate®
0 40-140
© 60-138
/
© 30-460
© 148-230
© 0.03-0.2
2.1 H ft3 per
charge
900 M ft3 per
quench
Water usually
sluiced; flow
variable and
cyclic
® 297-397
® 362-434
Temperature F
390 at throat
3000 at Furnace
100-400
100-300
<1832
140-150
245-258
Moisture: Vol %
9.6
2-10
Variable
depending on
point in coking
cycle
Effluent con-
sists primarily
of steam
6.4
- - - - - — — — — — — — ~-
Reduced Species Present in Primary Effluents
Cited From Literature
©
H2
H2S
©
Ni(CO)d, HCN, NH3
HzS, HJ, COS, CS,,
NH.CN f
*t
© ©
Ni(CO)4, HCN, HZ,
NH,, NH.CN, COS, CS.
J f f.
©
Cyanide and ammonia
species are cited in
the literature.
Distinct compounds
are not identified.
©
Cr(CO)e has been
cited in the litera-
ture, although this
is not a reducing
atmosphere.
Probable Stream
Based on Chemistry
©
FeS, HgS, MnS
COS, CaS, Fe(CO)5, Hn (CO)1Q
©
COS, Fe(CO),
D
'•-'
COS, Fe(CO),
3
©
AsH3, SbH3
The formation of a variety of
hydrides^ carbonyl , and metal
sulfides is possible.
© ©
The formation of a variety of
hyjrides, carbonyl s, and metal
sulfides is possible.
©
Metal sulfides, cyanides.
sulfur cyanides, and reduced
ammonia species.
©
If, however, the formation of
Cr(CO)e is possible, the
existence of other carbonyl s
is also possible. CO concen-
trations may be as high as
70 ppm.
l) Flow rate is expressed in: @ M SCFM or © M SCF/ton of product processed.
)- gaseous phase; (D - liquid phase;®- solid phase
-------
Process Identification
Refinery Operations
(a) Claus Plant
Tall Gas '
® Fixed Bed
Catalyst
Regeneration
© Moving Bed
Catalyst
Regeneration
(3) Fluid Coker
off-gas
Coal Conversion^-'
0 Gasification and
Liquefaction
Operations
®rnal
I»UCI 1
Preparation
© Quenching
and
Cooling
(3) Fixed bed
Effluent Characteristics From Predominant Process Operations
Particulate Data
Size
Distribution
gr/SCF
Flow Rate
-
Temperature °F
Fixed and mov-
ing bed regen-
erable cata-
lysts function
at about 850
to 1000°F at
300 to
700 psig
Moisture: Vol *
Catalyst: Same parameters and species as defined under "Refinery Operation," above.
Regeneration
© Sulfur
Plant: Same as Claus Plant above.
(D Tar
Separation
Fertilizer Manufacturer
6.3% < 5u.
12% < lOu,
29% < 30u,
34* < 40u
0.7 to 4.0
© 16.5
(one
unit)
201
Reduced Species Present in Primary Effluents
Cited from Literature
©
HzS, COS, CS2, NH3,
HCN
HzS, COS, CS2,
Ni(COU [Co(CO)4]2
H2S, COS, CS2, MHs,
N1(CO)4, HCN
H,S, COS. CS2, NH3,
RCN. Ni(CO)4
Sulfides in rinse
solution and par-
ticulate. The full
spectrum of reduced
species are formed
in gasification.
Many of these are
incorporated into
the quench water.
©
Ni(CO)4, NH4CN, HCN
©
NH3, HF
Probable Stream
Based on Chemistry
© ©
Spent chemicals from acid gas
amine solution regeneration =
carbonyls, cyanides, sul fides.
Mo(CO)6; the formation of vari-
ous metal sulfides, hydrides
and carbonyls probable.
Metal sulfides and carbonyls
probable.
Dryer off gases may contain
carbonyls.
©
The existence of Arsine, Stiblne,
carbonyls and sulfides is
probable.
©
Cyanides, Nitrosyls.
Stream parameters are highly variable depending on process design, see text.
-------
Process Identification
Forest Products
Industry
© Kraft Pulp Mills
© recovery
furnace
© lime kiln
© smelt
dissolving
Primary Nonferrous
Metals Industries
© Copper
© roasting
furnace
© electrolytic
refining
© Lead
© sinter
machine
© Blast
furnace
© Zinc
© roaster
© sinter
machine
© Aluminum
© reduction
cell
Effluent Characteristics From Predominant Process Operations
Particulate Data
Size
Distribution
50-85% < 2u
95% < 25u
90% < 5u
15% < lOw
100% < 10u
0.03 to 0.3
14% < 5,
31% < 10
70% < 20
100% < 10
Submicron
paniculate
gr/SCF
3-8
avg. 3-8
3-20
0.17-1.3
6-24
0.4-4.5
1-11
5-65
0.4-4.5
0.03-2.0
Flow Rate
0 20-568
© 278-568
® 7-50
45 SCF/air
dried ton
© 60-131
© 140
© 130
6-14
25-30
140
2000 to 4000
CFM/cel I
Temperature °F
270-650 avg.
350
400-900
170-200
600-890
250-600
150-250
730-900
320-700
Moisture: Vol %
20-40
400-600 Ibs/air
dried ton
670 Ibs/air
dried ton
Dew Point:
122-140
Reduced Species Present in Primary Effluents
Cited from Literature
©
H2S, Na2S
V
©
H2S, Na?S
©
Cu2S FeS
©
PbS
©
ZnS
©
H2S
Probable Stream
Based on Chemistry
©
COS FeS
COS, FeS, MgS, CaS
©
Liquid tailings from refining
operations are likely to con-
tain selenides, tellurides,
and sul fides.
©
PbS, ZnS
ZnS, CdS, COS
©
ZnS, PbS, CdS
COS, NagS, CaS, A12S3
Electrode is roncerned in the
reduction process; consider-
able CO is formed. Metal
carbonyls may therefore result.
Process data for electrolytic refining is highly variable; literature does not site specific flow data.
-------
present in the effluent of steel plant blast furnaces. The blast furnace
effluent may also contain FeS, MgS, MnS, COS, CaS, Fe(CO)5 and Mn(Cq)1Q.
The sinter plant may also discharge COS and Fe(CO)g.
Figure 2-1 shows the principle elements of an average steel plant
blast furnace and sintering machine. Solid samples in the form of
integrated composites may be obtained at the dust catcher and precipitator
(points 1 and 3, respectively) of the furnace. The sintering machine has
logical sampling points for integrated composite solid samples at the dust
bins (point 1) and the cyclones (point 2).
Integrated composite liquid samples may be obtained from the gas
washer (point 2) of the furnace. Particulate matter can be obtained by
sampling the stack gas effluents of both processes. Fugitive gas emissions
may be sampled from the surrounding area using a number of techniques
discussed in Section 3.0.
2.2.2 Coke Ovens
Coke ovens are also integral parts of most steel plants, but their
effluents have received significantly more attention than effluents from
other portions of the plants. Amoung the reduced species which have been
identified in the literature are: Ni(CO)4; HCN; NH3; H2S; H2; COS; CS2,
and NH^CN. Other hydrides (e.g., AsH3 and SbHg), metal carbonyls, cyanides,
and sulfides may be present in the gaseous and liquid effluent streams
based on the process chemistry.
The gaseous effluents from coke ovens (see Figure 2-2 for a typical
installation) may be sampled at the stack to obtain particulate matter
and near the oven slots to determine fugitive emissions. An integrated
composite liquid sample may be obtained at the sour quench water effluent
(point 3 on Figure 2-2).
2.2.3 Coal-Fired Boilers
Although coal-fired boilers are not operated under reducing conditions,
Cr(CO)6 has been cited in the literature as a constituent of the gaseous
effluent from the process. The presence of Cr(CO)g suggests the possible
8
-------
DUST COLLECTOR
DUCT
IGNITION FURNACE
SINTER BED
WIND
BOX
DUSTBINS' r.^ (2) FAN'
SINTERING MACHINE AND ASSOCIATED DUST COLLECTION SYSTEM.
BLAST FURNACE
ELECTROSTATIC PRECIPITATOR
TWO COMPARTMENTS
BLAST FURNACE AND ASSOCIATED DUST COLLECTION SYSTEM (TYPICAL).
FIGURE 2-1A Blast Furnace and Sintering Machine With
Associated Dust Collection System
-------
POTENTIAL PROCESS SAMPLES
® SOLID: INTEGRATED COMPOSITE
® LIQUID: INTEGRATED COMPOSITE
® SOLID: INTEGRATED COMPOSITE
0 GAS: PARTICULATE MATTER
® GAS: FUGITIVE EMISSIONS
® SOLID: INTEGRATED COMPOSITE
® SOLID: INTEGRATED COMPOSITE
® GAS: PARTICULATE MATTER
® GAS: FUGITIVE EMISSIONS
PROCESS
IDENTIFICATION
1) STEEL PLANT
©BLAST FURNACE
® SINTER PLANT
©WINDBOX:
©DISCHARGE
END:
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE
SIZE
DISTRIBUTION
15-90% < 74 x
14-45% < 40 p
9-30% < 20,i
4-19% < 10p
1-10% < SM
80% < lOOp
10% < 10|*
DATA
»r/SCF
4-30,
7-10 AVG.
0.2-3.2
1-5
FLOW RATE®
® 40-140
® 60-138
0 30-460
® 148-230
® 0.03-0.2
TEMPERATURE *F
390 AT THROAT
3000 AT FURNACE
100-400
100-300
MOISTURE: VOL%
9.6
2-10
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM
LITERATURE
©
Hj
HjS
PROBABLE STREAM
BASED ON CHEMISTRY
f»S, MgS, MnS '
COS, CoS, MCO)5, Mn (CO),0
COS, F,(CO)5
©
COS, F.(CO)5
FIGURE 2-1B Blast Furnace and Sintering Machine with
Associated Dust Collection System
-------
©
FIGURE 2-2A Coke Oven Battery
-------
ro
PROCESS IDENTIFICATION
(b) COKE OVENS
OOVEN OFF
GAS
(?) QUENCH
^ TOWER
(3) SOUR
^^ QUENCH
WATER
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
HIGHLY
VARIABLE
95-97%
>(J f
NOT
APPLICABLE
sr/SCF
1-15
0.05-0.1
FLOW RATE
2. 1 M FT3 PER
CHARGE
900 M FT3 PER
QUENCH
WATER USUALLY
SLUICED; FLOW
VARIABLE AND
CYCLIC
TEMPERATURE «F
< 1832
140-150
MOISTURE: VOL %
VARIABLE
DEPENDING ON
POINT IN COKING
CYCLE
EFFLUENT CON-
SISTS PRIMARILY
OF STEAM
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
©
Ni(CO)4, HCN, NH3
H2S, H2, COS, CS2,
NH4CN
©0
Ni(CO)4, HCN, H2,
NH3, NH4CN, COS, CSj
©
CYANIDE AND AMMONIA
SPECIES ARE CITED IN THE
LITERATURE. DISTINCT
COMPOUNDS ARE NOT
IDENTIFIED.
PROBABLE STREAM
BASED ON CHEMISTRY
©
A,H3, SbH3
THE FORMATION OF A VARIETY OF
HYDRIDES, CARBONYL, AND
METAL SULFIDES IS POSSIBLE.
©©
THE FORMATION OF A VARIETY
OF HYDRIDES, CARBONYLS, AND
METAL SULFIDES IS POSSIBLE.
©
METAL SULFIDES, CYANIDES,
SULFUR CYANIDES, AND
REDUCED AMMONIA SPECIES.
POTENTIAL PROCESS SAMPLES
0 GAS: PARTICULATE MATTER
© GAS: FUGITIVE EMISSIONS
OD LIQUID: INTEGRATED COMPOSITE
FIGURE 2-2B Coke Oven Battery
-------
formation of other metal carbonyls under similar conditions.
The metal carbonyls cited in the literature may be sought in the
fugitive emissions from the boilers and by sampling the stack gases. The
inherent Instability of metal carbonyls will make sampling with a goal
of subsequent compound identification very difficult if not impossible.
2.2.4 Refinery Operations
Many of the operations commonly performed during the refining of
crude oil and other associated processes are conducted under reducing
conditions. The nature of the effluents from these operations have been
the subject of several investigations. A partial list of the species
reported (see Table 2-1 for a more complete list of species and specific
effluent streams) are: H2$; COS; C$2; NH3; HCN; Ni(CO)4 and [Co(CO)4]2.
Other carbonyls, cyanides, sulfides and hydrides are suspected in the
gaseous and liquid effluent streams.
Time integrated gas samples may be taken at a number of points in a
typical refinery complex (Figure 2-3) to trap gaseous reduced species.
The hydrocracking and catalytic cracking units (points 1 and 2, respectively)
are typical locations, as are the asphalt still (point 5) and the sulfur
plant (point 6). In some instances specific on-line measurement techniques
may be useful. On-line methods should be employed whenever possible, since
the high reactivity of many of the reduced inorganic species of interest
may lead to erroneous results if conventional integrated bag or metal
container samples are used or if analysis is delayed. Also the on-line
method provides process variation and up-set information not normally
observed during sampling visits.
Particulate matter samples may be obtained from the gas streams of the
coker (point 3) and catalytic reforming untt (point 4). Fugitive emtsions
can only be determined by a sampling matrix designed for each individual
plant, not generalized to the industry.
2.2.5 Coal Conversion
A number of coal liquifaction and gasification processes are now in
13
-------
DRY GAS
WET GAS
CRUDE OIL
•• FUEL GAS
MOTOR GASOLINE
AVIATION GASOLINE
KEROSENE
LIGHT FUEL OIL
-H POLY PLANT
I POLY GASOLINE ,
*^ HVY HYDRO-
CRACKED
GASOLINE
•-GREASES
HEAVY FUEL OIL
FIGURE 2-3A Processing Plant for Typical Complete Refinery
-------
POTENTM*. PROCESS SAMPLES
0 GAS: TIME INTEGRATED
/7\
GAS: TIME INTEGRATED
GAS: PARTICULATE MATTER
GAS: PARTICULATE MATTER [FROM CATALYST REGENERATION]
GAS: TIME INTEGRATED
GAS: TIME INTEGRATED
GAS: FUGITIVE EMISSIONS [PLANT MATRIX]
PROCESS IDENTIFICATION
RERNERY OPERATIONS
© CLAUS PLANT
TAIL GAS
FIXED BED
CATALYST
REGENERATION
© MOVING BED
<"ATAIYST
REGENERATION
(3) FLUID COKER
OFF -GAS
EFFLUENT CHARACTERISTICS
FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
8r/SCF
FLOW
RATE
TEMPERATURE *F
FIXED AND MOV-
ING BED REGEN-
ERABLE CATA-
LYSTS FUNCTION
AT ABOUT 850 TO
1000 'F AT 300 TO
700PSIG
MOISTURE:
VOL%
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
(g)
H,S, COS, CS,, NH-,
HCN
H2S, COS,
-------
various stages of development. The chemistry and operating condition of
the various processes differ significantly, however all of the conversion
processes involve operations which take place under reducing conditions.
A wide spectrum of reduced species, both organic and inorganic, can be
expected in the gaseous, liquid and solid effluents of these processes.
Table 2-1 lists some specific examples, however the identities and relative
quantities of the reduced inorganic species emitted from a process will be
site specific.
The Lurgi process was chosen as an example to illustrate the location
of potential sampling points in a coal gasification complex (Figure 2-4).
Integrated composite solid samples may be taken from the ash produced in the
gasifier (points 3 and 2). Time integrated gas samples should be obtained
from the aqueous streams produced in the purification and treatment
operations. It is also important to trap particulate matter present in
the gaseous effluent from the coal preparation (point 1) and catalyst
regeneration (point 11) operations. A carefully designed sampling matrix
should be implemented to determine fugitive emmisions.
Figure 2-5 shows the principle operations of a typical coal liquefaction
complex. A sampling matrix to determine fugitive emissions is appropriate,
as is the obtaining of integrated composite liquid samples from all of the
effluent aqueous streams. Of particular importance is an integrated
sample of spent scrubber solution (point 6). Particulate matter in the
gas streams from the coal preparation, catalyst regeneration and preheater
units should be sampled. Gaseous effluents should be determined by
obtaining a time integrated gas sample from the stack of the gas treatment
units (point 5).
2.2.6 Fertilizer Manufacturing
Ammonium nitrate is the principal, commercially produced, synthetic
fertilizer. Ammonia and hydrogen fluoride have been reported as present
in the effluents from nitrate fertilizer manufacturing. The conditions
normally employed in the production of ammonium nitrate may also result in
the formation of cyanides and nitrosyls.
Nitrate fertilizer plants (Figure 2-6) should be sampled for fugitive
16
-------
AIR-
SULPHUR
LURGI
GASIRER
445 KIG
COAL
PREPARATION
0
AIR-
LURGI
GASIRER
28SPSIG
STEAM ASH
STEAM ASH
©
^ ELECTRICITY
106 TPH (1/3 PLANT
STEAM REQUIREMENTS)
SCF.
POWER,
STEAM
PLANT
WATER
METHANATION
(60%OFCH4
PRODUCTION)
H COMPRESSION
PIPELINE GAS
754 ITU/SCF.
FIGURE 2-4A Simplified Gasification Complex (LurgO
-------
00
PROCESS IDENTIFICATION
COAL CONVERSIONvL/
(a) GASIFICATION AND
LIQUEFACTION
OPERATIONS
(?) COAL
^ PREPARATION
©QUENCHING
AND
COOLING
(3) FIXED BED
^ CATALYST: SAM
REGENERATION
©SULFUR
PLANT: SAf
(5) TAR
v-x SEPARATION
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
PARAMETERS Al
IE AS CLAUS PU
gr/SCF
ID SPECIE
NT ABOV
FLOW RATE
5 AS DEFINE!
:
TEMPERATURE «F
' UNDER "REFINERY
MOISTURE: VOL %
OPERATION," ABOVE.
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
SULFIDES IN RINSE
SOLUTION AND PAR-
TICULATE- THE FULL
SPECTRUM OF REDUCED
SPECIES ARE FORMED
IN GASIFICATION.
MANY OF THESE ARE
INCORPORATED INTO
THE QUENCH WATER.
CL)
Ni(CO)4, NH4CN, HCN
PROBABLE STREAM
BASED ON CHEMISTRY
DRYER OFF GASES MAY CONTAIN
CARBONYLS.
_
\tj
THE EXISTENCE OF ARSINE, STIBINE,
CARBONYLS AND SULFIDES IS
PROBABLE.
0 STREAM PARAMETERS ARE HIGHLY VARIABLE DEPENDING ON PROCESS DESIGN, SEE TEXT.
POTENTIAL PROCESS SAMPLES
© GAS: PARTICULATE MATTER
© SOLID: INTEGRATED COMPOSITE
© SOLID: INTEGRATED COMPOSITE
© GAS: FUGITIVE EMISSIONS MATRIX
© GAS: TIME INTEGRATED
© GAS: TIME INTEGRATED
© GAS: TIME INTEGRATED
® LIQUID: INTEGRATED COMPOSITE
® GAS: TIME INTEGRATED
© LIQUID: INTEGRATED COMPOSITE
(vf)
GAS: PARTICULATE MATTER [CATALYST REGENERATION]
FIGURE 2-4B Simplified Gasification Complex (Lurgl)
-------
VENT GASES
WATER
SULFUR
FUEL GASES
\T
RICH GAS RECYCLE GAS
RICH GAS COMpRESSOR
GAS TREATMENT
AND SEPARATION
COAL
PREPARATION
LET DOWN AND
FLASH SYSTEM
REACTOR
(DISSOLVED
850° F
1000 PSI
SUPPLEMENTAL
COAL
SLURRY
PREPARATION
;SOLID/LIQUID
SEPARATOR
(FILTER)
FIRED
PREHEATER
HYDROGEN
PRODUCTION
FRESH HYDROGEN
MINERAL
MATTER
SLURRY FEED
PUMP
SOLVENT
RECOVERY
SOLVENT RECYCLE
SOLIDIFICATION
AND SOLVENT
RECOVERY
SOLID
FUEL
(SRC)
FIGURE 2-5A Simplified L1qu1fact1on Complex (SRC)
-------
POTENTIAL PROCESS SAMPLES
Cl) GAS: PARTICIPATE MATTER
0
(D
©
(T)
GASs PARTICULATE [CATALYST REGENERATION]
GAS: PARTICULATE MATTER
LIQUID: VARIOUS SOUR WATER STREAMS; TIME INT.
GAS: TIME INTEGRATED
LIQUID: INTEGRATED COMPOSITE [SPENT SCRUBBER SOLUTION]
GAS: FUGITIVE EMISSIONS MATRIX
PROCESS IDENTIFICATION
COAL CONVERSION vi/
(a) GASIFICATION AND
^ LIQUEFACTION
OPERATIONS
(?) COAL
v-x PREPARATION
(2) QUENCHING
^ AND
COOLING
(?) FIXED BED
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS
OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
gr/SCF
FLOW RATE
TEMPERATURE
°F
MOISTURE:
VOL%
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
SULFIDES IN RINSE
SOLUTION AND PAR-
TICULATE. THE FULL
SPECTRUM OF REDUCED
SPECIES ARE FORMED
IN GASIFICATION.
MANY OF THESE ARE
INCORPORATED INTO
THE QUENCH WATER.
^ CATALYST! SAME PARAMETERS AND SPECIES AS DEFINED UNDER "REFINERY OPERATION, " ABOVE.
REGENERATION
(7) SULFUR
^ PLANT: SAME A
(s) TAR
^ SEPARATION
S CLAUS PLANT
ABOVE.
/"N
Ni(CO)4, NH4CN, HCN
PROBABLE STREAM
BASED ON CHEMISTRY
DRYER OFF GASES MAY CONTAIN
CARBONYLS.
Ck)
THE EXISTENCE OF ARSINE, ST1BINE,
CARBONYLS AND SULFIDES IS
PROBABLE.
ro
O
STREAM PARAMETERS ARE HIGHLY VARIABLE DEPENDING ON PROCESS DESIGN, SEE TEXT.
FIGURE 2-5B Simplified L1qu1fact1on Complex (SRC)
-------
(NITROGEN OXIDES, NH4NO3, HjO,
ro
HNO,
AMMONIA
NEUTRALIZER
EVAPORATOR DRYER
EXIT
(NH3/ NITROGEN OXIDES)
(PARTI CULATES)
0
SCRUBBER
WATER
GRANULATOR
AMMONIUM NITRATE TO .
STORAGE AND PACKAGING
FIGURE 2-6A
Flow Diagram of The Process for Manufacture of Ammonium Nitrate
-------
POTENTIAL PROCESS SAMPLES
GAS: PARTICIPATE MATTER
LIQUID: INTEGRATED COMPOSITE
GAS: FUGITIVE EMISSIONS [PLANT MATRIX]
PROCESS IDENTIFICATION
FERTILIZER MANUFACTURER
EFFLUENT CHARACTERISTICS
FROM PREDOMINANT PROCESS OPERATIONS
PARTI CULATE DATA
SIZE
DISTRIBUTION
6.3% < Sn,
12% < 10|i,
29% < 30fi,
34% < 40«,
gr/SCF
0.7 TO 4.0
FLOW RATE
©16.5
(ONE
UNIT)
TEMPERATURE °F
201
MOISTURE:
VOL%
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
(§)
NH3, HF
PROBABLE STREAM
BASED ON CHEMISTRY
(5)
CYANIDES, NITROSYLS
ro
ro
FIGURE 2-6B
Flow Diagram of The Process for Manufacture of Ammonium Nitrate
-------
gaseous emissions. The gaseous stream emanation from the scrubber (point 1)
should be sampled to obtain particulate matter and an integrated composite
liquid sample should be obtained from the aqueous effluent streams.
2.2.7 Forest Products
Paper is the major non-wood product of the forest products industries
and the Kraft process (Figure 2-7) is employed in the production of a
significant portion of that product. Kraft pulp mills produce a number of
reduced species of interest, even though many of the operations involved
are actually oxidation. H2S and Na2S are the two reduced inorganic
species which have been repeatedly cited In the literature as being
present 1n the effluent of Kraft mills. It 1s also probable that COS,
FeS, MgS, and CaS are produced in the process and are present in the
effluent.
Time integrated gas samples may be taken at the digester (point 1),
blow heat recovery unit (point 7), form tank (point 5), multiple-effect
evaporator (point 3) and the lime kiln (point 11). Fugitive gas emissions
may be determined by a plant matrix and at some specific sources subject
to equipment leaks (e.g., point 8). Particulate samples from the gas
stream emanating from the electrostatic precipitator (point 2) should be of
interest. Integrated composite liquid samples may be taken from the aqueous
streams coming from the multiple-effect evaporator (point 4), the blow tank
heat recovery unit (point 6) and the screens (point 9).
2.2.8 Primary Nonferrous Metals
The primary nonferrous metals group includes copper., lead, zinc, and
aluminum. There is considerable variation in the processes used to make
each of these metals, and in some instances particularly in aluminium there
are new processes under development which differ significantly from those
currently in vogue. However, the simplified flow diagrams show in Figures
2-8 to 2-11 represent typical plants for which information is now
available.
23
-------
ro
SIMPLIFIED KRAFT MILL FLOW DIAGRAM. 1, DIGESTER; 2, BLOW TANK;
3, BLOW HEAT RECOVERY; 4, WASHERS; 5, SCREENS; 6, DRYERS; 7, OXIDATION TOWER;
8, FORM TANK; 9, MULTIPLE-EFFECT EVAPORATOR; 10, DIRECT EVAPORATOR; 11, RE-
COVERY FURNACE; 12, ELECTROSTATIC PRECIPITATOR; 13, DISSOLVER; 14, CAUSTICIZER;
15, MUD FILTER; 16, LIME KILN; 17, SLAKER; 18, SEWER.
FIGURE 2-7A Simplified Kraft Mill Flow Diagram
-------
POTENTIAL PROCESS SAMPLES
V) GAS: TIME INTEGRATED
GAS: PARTICULATE MATTER
*) GAS: TIME INTEGRATED
*) LIQUID: INTEGRATED COMPOSITE
GAS: TIME INTEGRATED
© LIQUID: INTEGRATED COMPOSITE
(Y) GAS: TIME INTEGRATED
© GAS: FUGITIVE EMISSIONS [SPECIFIC SOURCE]
© LIQUID: INTEGRATED COMPOSITE
|JO) GAS: FUGITIVE EMISSIONS [PLANT MATRIX]
(fl) GAS: TIME INTEGRATED
PROCESS IDENTIFICATION
FOREST PRODUCTS
INDUSTRY
0 KRAFT PULP MILLS
(7) RECOVERY
^ FURNACE
© LIME KILN
(3) SMELT
^ DISSOLVING
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
50-85% < 2 It
95% < 25 H
90% < 5M
gr/SCF
3-8
AVG. 3-8
3-20
0.17-1.3
FLOW RATE
0 20-568
0 278^568
0 7-50
45 SCF/AIR
DRIED TON
TEMPERATURE °F
270-650 AVG.
350
400-900
170-200
MOISTURE: VOL %
20-40
400-600 IBS /AIR
DRIED TON
670 LBS/AIR
DRIED TON
REDUCED SPECIES PRESENT
IN PRIMARY EFFLUENTS
CITED FROM
LITERATURE
©
H2S, NajS
©
H2S
©
HjS, Na2S
PROBABLE STREAM
BASED ON CHEMISTRY
COS FeS
©
COS, FeS, MgS, CaS
ro
ui
FIGURE 2-7B Simplified Kraft M111 Flow Diagram
-------
Copper --
The literature identified Cu2S and FeS as present in the effluent
from copper roasting furnaces and AsH3 as emanating from the electrolytic
refining unit. It is also likely that liquid tailings from refining
operations will contain selenides, tellurides and sulfides.
Appropriate liquid sampling points at a copper smelting plant (Figure
2-8) are the quench tank (point 3), the scrubber (point 4) and the refining
operations (point 7). Integrated gas samples should also be taken at
the refining operation (point 7) and at the acid plant (point 6). A plant
sampling matrix to ascertain the level of fugitive emissions should also be
performed and a sample of particulate matter in the gas stream from the
electrostatic precipitators (points 1 and 5) should be obtained.
Lead —
Lead sulfide has been reported to be present in the gaseous effluent
from the lead blast furnace (Figure 2-9). In addition, this stream may
also contain ZnS, CdS and COS. The sinter machine is also likely to be a
source of PbS and ZnS.
Points 1,2,3 and 4 are suggested for sampling particulate contained in
gas streams. A plant sampling matrix to determine fugitive gaseous
emissions may also be performed.
Zinc --
Zinc sulfide has been found in the effluent from the roasting operation
(Figure 2-10). ZnS along with PbS and CdS are likely to be found 1n
the sinter machine effluent also. Integrated composite solid samples
may be obtained from Points 2 and 4. The stacks from the dust collection
system (point 1) and roasting furnace (point 3) operations may be sampled
for particulate.
Aluminium —
Hydrogen sulfide is the only reduced inorganic compound identified in
literature as present in the effluent from aluminium refining operations.
It is also likely based on the chemistry of the process that COS, Na2S,
CaS, A12S3, and various metal carbonyls will be present. Potentially
useful areas to obtain process samples (Figure 2-11) are the potline
26
-------
(time integrated gas sample and fugitive emissions) and the scrubbers
(particulate matter from the exhaust and an integrated composite liquid
sample).
27
-------
CONCENTRATE
ro
oo
FLUX
ATMOSPHERE
CONCENTRATE
STORAGE BINS
FLUX
STORAGE BINS
•PROCESS DATA FOR ELECTROLYTIC REFINING IS HIGHLY VARIABLE; LITERATURE DOES NOT
SITE SPECIFIC FLOW DATA
FIGURE 2-8A Copper Smelting - Simplified Flow Diagram
-------
POTENTIAL PROCESS SAMPLES
2) GAS: PARTICULATE MATTER
g) GAS: FUGITIVE EMISSIONS [SPECIFIC SOURCE]
§) LIQUID: INTEGRATED COMPOSITE
g) LIQUID: INTEGRATED COMPOSITE
g) GAS: PARTICULATE MATTER
(§) GAS: TIME INTEGRATED
5)© LIQUID: INTEGRATED COMPOSITE
® GAS: TIME INTEGRATED
PROCESS IDENTIFICATION
PRIMARY NONFERROUS
METALS INDUSTRIES
0 COPPER
(?) ROASTING
^ FURNACE
/?> ELECTROLYTIC
Vi/ REFINING*
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DA
SIZE DISTRIBUTION
15% < 10
TA
*/SCF
6-24
FLOW RATE
0 60 - 131
TEMPERATURE °F
600-890
MOISTURE: VOL %
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM
LITERATURE
©
Cu2S F.S
AtHj
PROBABLE STREAM BASED ON CHEMISTRY
LIQUID TAILINGS FROM REFINING
OPERATIONS ARE UKELY TO CON-
TAIN SELENIDES, TELLUR4DES,
AND SULFIDES.
r\>
vo
FIGURE 2-8B Copper Smelting - Simplified Flow Diagram
-------
CJ
o
LEAD SILICEOUS CRUDE
CONCENTRATED ORE- | ORE*
si
4
1
{PRESSURE LEACHING
| ^C«SO4, ZnSO4SOLUTIO
1 1 TO ZINC PLANT OR SOL
|AUTm.lAVt| f^ BF^nvfBV
[PbSO.RESIDUE
"
" I
RETURN
SINTER
|
. ZINC PLANT
1 RESIDUE I LIMEROCK*
~\
N
VENT
ROLYTIC
H
1
1 SLAG*
1 IY-PRODUCTS*i
•THESE PRODUCTS ARE ALL CRUSHED AND
GROUND IN A ROD MILL TO -1/B IN. SIZE
h» ©
4"
[CHARGE PREPARATION)
I
| PELLETIZING 1 o>
1 1 D & L SINTERING | ' »] (
COKE
SLAG SHELL
COAL
LOW GRADE ZnO 1 „„..,,,-„..„
I
* i
•flSfnFinf «cHDfLEADING KliN)
TO MARKET |
DELEADED ZINC
OXIDE TO MARKET
DEZINCED GRANULATED «.
SLAG TO STORAGE
AG TO BLAST FURNACE
I
PARKES SILVER CRUST 4
| RETORTS | | RETORTS |
i V
| CUPEL | | CUPEL |
11 14 SLAG TO
1 » T .IAST
Iftl &{
« SLAG
rOTTRELL |
SINTER REFINERY DROSSES
1
BULLION
| COPPER
CONCENTRATION FOR CADMIUM-
EXTRACTION ELECTRIC FURNAa
DROSS
41 4
I
BULLION
i BL
1 SOFTENING FURNACE
BULLION
1
zn — i
H DESILVERIZING 1
GOLD KETTLE I
i
1 DESILVERIZING IZINC
1 SILVER KETTLE 1
("VACUUM DEZINCING I*'™-!
| KEHLE
1 r NoOH
| REFINING KETTLE |
CASING1 ^°
» MiVrt «»« BAGHOUSE
5|A
-------
POTENTIAL PROCESS SAMPLES
(7) GAS: PARTICULATE MATTER
(2) GAS: PARTICULATE MATTER
(7) GAS: PARTICULATE MATTER
(4) GAS: PARTICULATE MATTER
(i) GAS: FUGITIVE EMISSIONS [PLANT MATRIX]
•
PROCESS
IDENTIFICATION
(b) LEAD
(7) SINTER
v-x MACHINE
©BLAST
FURNACE
EFFLUENT CHARACTERISTICS FROM PREDOMINANT
PROCESS OPERATIONS
PARTI CULAT
SIZE
DISTRIBUTION
100% < 10M
0.03 TO 0.3
EDATA
gr/SCF
0.4-4.5
1-11
FLOW RATE
(a) 140
(£) 130
6-14
TEMPERATURE
°F
250-600
150-250
MOISTURE:
VOL %
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
(§)
PbS
PROBABLE STREAM
BASED ON CHEMISTRY
(§)
PbS, ZnS
ZnS,CdS, COS
FIGURE 2-9B Typical Flowsheet of PyrometaTlurglcal Lead Smelting
-------
to
ro
SIZE I-H BLEND HH SHAPE 1-*^ DRY hH PREFIRE
CONCENTRATES
BLEND
SINTER
STACK 0
OUST
COLLECTION
SINTER I COAL
WI-LUAC3
vv
MAGNETIC /^\
ROASTING
ZINC: PLATES
ZINC: SPECIAL SHAPES
ZINC: DUST
-— ZINC, SHG: PLATES
BALLS
JUMBOS
•• DIE CAST ALLOYS
— CADMIUM: BALLS
STICKS
ANODES
RESIDUE
INGOTS
FIGURE 2-1OA Zinc Smelting Flow Diagram
-------
POTENTIAL PROCESS SAMPLES
0 GAS: PARTICIPATE MATTER
0 SOLID: INTEGRATED COMPOSITE
0 GASs PARTICULATE MATTER
0 SOLID: INTEGRATED COMPOSITE
(§) GAS: FUGITIVE EMISSIONS [PLANT MATRIX]
PROCESS IDENTIFICATION
© ZINC
© ROASTER
(g) SINTER
MACHINE
EFFLUENT CHARACTERISTICS FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
14% < 5
31% < 10
70% < 20
100% < 10
gr/SCF
5-65
0.4-4.5
FLOW RATE
25-30
140
TEMPERATURE °F
730-900
320-700
MOISTURE: VOL%
DEW POINT:
122-140
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
CITED FROM LITERATURE
ZnS
PROBABLE STREAM
BASED ON CHEMISTRY
©
ZnS, PbS, CdS
FIGURE 2-1 OB Z1nc Smelting Flow Diagram
-------
ROOF MONITORS
FUMES NOT
CAPTURED BY POTLINE
HOODING
ANODE BUS BAR
u>
GAS COLLECTION
HOOD
ALUMINA
HOPPER
EXHAUST TO
POTLINE SCRUBBERS
GAS AND FUME
EVOLUTION
CRUST
<
FARBON
. ANODE
'•Vx— ---- •
MOLTEN ELECTROLYTE
ALUMINA
MOLTEN ALUMINUM
CARBON LINING
INSULATION
CATHODE (-)
COLLECTOR
BARS
FIGURE 2-11A Aluminum Cell (Prebaked Anode Type)
-------
POTENTIAL PROCESS SAMPLES
© © GAS: TIME INTEGRATED
© GASs FUGITIVE EMISSIONS [SPECIFIC SOURCE]
© © GAS: PARTICIPATE MATTER [ON EXHAUST]
® LIQUID: INTEGRATED COMPOSITE
PROCESS IDENTIFICATION
0 ALUMINUM
0 REDUCTION
CELL
EFFLUENT CHARACTERISTICS
FROM PREDOMINANT PROCESS OPERATIONS
PARTICULATE DATA
SIZE
DISTRIBUTION
SUBMICRON
PARTICULATE
gr/SCF
0.03-2.0
FLOW RATE
2000 to
4000 CFM/
CELL
TEMPERATURE °F
MOISTURE:
VOL%
REDUCED SPECIES PRESENT IN PRIMARY EFFLUENTS
Q TED FROM LITERATURE
©
H2S
PROBABLE STREAM
BASED ON CHEMISTRY
©
COS, Na2S, CaS, AljS3
ELECTRODE IS CONCERNED
IN THE REDUCTION PROCESS;
CONSIDERABLE CO IS FORMED.
METAL CARBONYLS MAY
THEREFORE RESULT.
FIGURE 2-11B Aluminum Cell (Prebaked Anode Type)
-------
Table 2-2
Selected References for Process Information
Vandegrift, et al, "Particulate Pollutant System Study", Volumes I,
II, and III. Midwest Research Institute, PB-203-521, May, 1971, 1,
314 pp.
A. Stern, ed., "Air Pollution", Volumes I, II, and III, Academic Press,
New York, 1968, 2, 244 pp.
J. Daniel son, ed., "Air Pollution Engineering Manual", U. S. Environ-
mental Protection Agency, R.T.P., May, 1973, 986 pp.
P. Westmoreland, et al, "Comparative Kinetics of High-Temperature
Reaction Between H?S and Selected Metal Oxides", Environmental Science
and Technology, Volume II, No. 5, May, 1977, 488-491.
A. J. Forney, et al, "Trace Element and Major Component Balances Around
the Synthane P.D.U. Gasifier", P.E.R.C., Pittsburgh, Pennsylvania,
PERC/TPR 75/1, August, 1975, 25 pp.
C. Schmidt, et al, "Mass Spectrometric Analysis of Product Water from
Coal Gasification", U. S. Department of the Interior BOM/TPR/86,
December, 1974, 7 pp.
C. Burklin, et al, "Control of Hydrocarbon Emissions from Petroleum
Liquids", Radian Corporation, EPA Contract No. 68-02-1312 T12,
September, 1975, 230 pp.
W. Fulkerson, ed., et al, "Ecology and Analysis of Trace Contaminants",
ORNL Progress Report, October, 1973 to September, 1974, 174 pp.
T. Hutchinson (coordinator), "International Conference on Heavy Metals
in the Environment", Toronto, Ontario, Canada, October, 1975, 627 pp.
H. Anderson and W. Wu, "Properties of Compounds in Coal-Carbonization
Products", B.O.M. Bulletin 606, U. S. GPO, Washington, D.C., 1963,
834 pp.
J. Dealy and A. Kill in, "Engineering and Cost Study of the Ferroalloy
Industry", Office of Air and Waste Management, EPA 450/2-74-008
(PB-236-762), May, 1974, 200 pp.
/
W. Beers, "Characterization of Claus^ Plant Emissions", Processes
Research, Inc., Cincinnati, Ohio, EPA Contract No. 68-02-0242 T2,
April, 1973, 121 pp.
H. Lebowitz, et al, "Potentially Hazardous Emissions from the Extrac-
tion and Processing of Coal and Oil", Battelle Columbus Laboratory,
NERC, PB 241-803, April, 1975, 153 pp.
36
-------
SECTION 3.0
SAMPLING TECHNIQUES FOR REDUCED INORGANIC SPECIES
The sampling procedures described in this section have been chosen for
the processes listed in Section 2.0 with a view toward obtaining samples
that will afford an analytical accuracy of ±25%. Simply stated, an accuracy
level of ±25% requires adherence to the following three practices:
• Samples must be time integrated to account for process operational
variances.
• Sampling techniques must be sensitive enough to measure volumes,
weights or flows with greater accuracy than *25%.
• Careful attention must be given to the avoidance of sample
contamination and/or loss.
The sampling techniques recommended in this study have been chosen to
characterize specific streams for the processes presented in Section 2.0
and include:
1) Solid: integrated conposite
2) Liquid: integrated composite
3) Gas: time integrated (non-particulate)
4) Gas: fugitive emissions
5) Gas: SASS train (particulate)
At this time certain general comments may be made concerning these
five techniques .with respect to obtaining samples containing reduced
inorganic species. Final decisions concerning exact sampling methods for
a site will require a more detailed study of the individual process
chemistry and stream parameters. Many of the methods eventually selected
will have to be novel techniques tailored to the characteristic unstable
-------
and/or reactive nature of many reduced inorganic species. The sampling
techniques selected for use must have the potential to maintain the
constituents of a sample in their original state or in a controlled
modified state which can then be related in a quantitative manner to the
original compound structure.
3.1 SOLID: INTEGRATED COMPOSITE
Solid samples may be obtained by using shovel or core sample techniques
over a time period representative of the cyclic nature of the process in
question. However, automatic sampling techniques should be used whenever
available if they meet the ±25% accuracy criterion. If the process is not
cyclic, samples should be taken at equally spaced time intervals for a
specified time period. The composite thus obtained should be reduced using
a coning and quartering technique to obtain a final sample for shipment to
the laboratory.
Coning and quartering consists of carefully piling the material into
a conical heap then flattening the cone into a circular cake. The cake
is then divided into quadrants with opposite quadrants being taken for the
representative sample and the other two discarded. The entire process can
be repeated until the desired sample size is obtained. This method is time
consuming and the symmetry of the intended vertical size segregation may
be difficult to achieve in practice. An alternative method is called
fractional shoveling, in which every third, fourth, fifth, or tenth
shovelful! is taken as a sample. This method 1s applicable to materials
being loaded, unloaded, or moved from one place to another by shoveling.
If performed conscientiously, fractional shoveling can be more reliable
than coning and quartering and is inexpensive and relatively fast.
3.2 LIQUID: INTEGRATED COMPOSITE
Accurate and representative liquid samples are best obtained by
collecting hourly increments of 0.25 liter. The total quantity of the
sample increments collected should be approximately 0.1% (but not more
than 105 liters) of the total quantity of the stream being sampled.
38
-------
If automatic samplers are available for the streams in question, they
should be used in accordance with the plant production schedule as a first
perference. Many liquid streams contain suspended particulate matter. If
an accuracy level of -2S% is to be obtained, these streams must be sampled
isokinetically using a time integrated continous sampling technique. There
are several designs for continuous sampling probes, a few examples are
shown in Figure 3-1 below.
45" BEVEL'
(A)
3.50 - 7.0 MM
(1/8 - 1/4 IN.) PIPE
TO RECEIVER
OR SAMPLER
-------
In order to obtain a representative fugitive emission sample from a
specific source it is important that:
• The sample be taken while the vent cycle is in progress.
(Cycle periods for individual processes should be known as a
result of a pre-test survey).
• The entrance nozzel of the sampling unit be situated in such a
way that a representative sample of the vent effluent is obtained
without contamination by ambient air.
Manufacturing, process, or transfer areas either enclosed or open are
major sources of fugitive emissions. Depending on the control devices in
use, the emissions can range from slightly above ambient to near stack gas
levels. In all cases, the duration of the sampling period should be
integrated with the cyclic nature of the processes.
In obtaining fugitive boundary samples, the perspective is considerably
altered with respect to the methods which apply to enclosed structure
sampling. Depending on the size of the plant in question, there may be a
multitude of isolated sources each of which contribute to the overall
emission. Atmospheric mixing will play a role in homogenizing individual
emission sources, but certainly not to a reliable and predictable degree.
It is generally recommended that at least four sample points be
established at equal distances apart in such a way that if the process under
investigation were quartered, each quarter would be represented by one
sampler. If the plant is larger, it can be divided into sixths with one
sampler for each sixth or more depending on the size of the installation
to be sampled. Consequently, in order to obtain reliable data the
decision as to the position and number of samplers and the sampling time
should be based on:
1) The analytical objectives for the acquired samples (if ±25%
analyses are to be performed, then sampling accuracy must be of
at least this order).
2) The total land area of the process in question (larger plants
will require a greater number of sampling points to provide the
proper coverage. Too few sampling points in a large plant could
miss emission point sources (stacks, vents, etc.) due to
40
-------
meteorological conditions).
3) The number of emission sources within the system (in order to
avoid a biased sample when many emission sources exist within
the plant boundaries, the number of sample points should be
increased).
4) The estimated average fugitive emission concentration (many
situations will require long sampling periods to obtain enough
sample for analysis. Thus, the time required to sample will
vary'inversely with emission concentrations).
5) The number of enclosed structures in which emission levels are
expected to be high (when more sources of different emissions
exist, the network of samplers may also have to be increased
to obtain representative samples).
6) Cyclic nature of emissions (most plants will have operations
that vary with time. The sampling team has the choice of
sampling for a period of time to overlap the cycles or to time
the sampling period to the cycle).
3.4 GAS: TIME INTEGRATED
Many reduced inorganic species of interest may be found in the gas
(non-particulate) phase. Special techniques will be required to sample for
these compounds. Conventional time integrated bag samples or metal sampling
systems probably will not prove to be adequate for traping reduced species
because of the unstable or reactive character that these compounds often
exhibit.
In view of the accuracy requirements (±25%) the samples will, however,
have to be time integrated. Chemical adsorption impinger sampling, or
on-line analysis when available, have the highest potential as sampling
techniques for gaseous effluents.
3.5 GAS: SASS TRAIN
The SASS train, as it is currently configured, is probably not a
41
-------
viable sampling tool for reduced inorganic species because of the materials
used in its construction. Sampling for solid inorganic species from
particulate material may be possible using the SASS train, however, reduced
inorganic gases will probably either be lost or chemically modified due
to their thermal instability or susceptability to oxidation.
In view of the wide spread use of the SASS train and the doubts
associated with the use of the SASS train to trap reduced inorganic species
in a state that is useful for subsequent analysis and identification, the
chemistry of some of the compounds of interest was studied in order to
prepare a map of the probable location of specific species in the train.
The following sections describe the results of the study.
3.5.1 SASS Distribution of The Hydrides; PH3> AsH3> and SbH3
The hydrides (phosphine, arsine, and stibine) can be formed in several
processes, for example, in a reducing acidic atmosphere when the respective
elements are present or by several electrolytic processes. The stability
of these hydrides decreases in the order, PH_ > AsH_ » SbH-j so that
stibine is very unstable, thermally decomposing to the metal under mild
heat.
In general, the SASS train would be ineffective for sampling these
highly reactive substances for subsequent compound identification while
sampling techniques which take advantage of the strong reducing character
of this series of gases would be perferable. The expected small concentration
of these compounds also dictates the use of micro techniques so that
subsequent analysis can be performed without excessive preconcentration.
A schematic representation of the probable distribution of the hydrides 1s
shown in Figure 3-2.
PH3 (Phosphine) —
Phosphine, the most stable of the hydrides studied, is not spon-
taneously flammable but is readily oxidized by air upon ignition. The
compound is exceedingly poisonous, sparingly soluble in water, and is a
strong reducing agent.
Based on the chemistry and volatility of phosphine, it is not expected
42
-------
200°CMAX
3ft
1
fkiks*Nfer
PROBE
1
1
CYCLONE
^.
CYCLONE
^
CYCLONE FILTER
COOLING
(20-Q
0
PH3
AsH3
SbH3
OrganometalHc forms of P, As, and Sb
L = Small concentration
M * Moderate concentration
H - Large concentration
XAD-2
SO WE NT
IMPINGERS
APS
APS
FIGURE 3-2 Probable Distribution of PH3, AsH3 and SbHg 1n the SASS Train
-------
to be found at any appreciable concentration in the probe, cyclones or
filter. Some PH3 may react with oxidizing agents, such af Fe (III), to
form H2P03 or H,PO. in the presence of water. This reaction is catalyzed
by base, but will proceed slowly even in a neutral or acidic medium. The
phosphine concentration is also expected to be small in the XAD-2 sorbent
trap because of rapid breakthrough. However, no chemical alternation
should take place at this point if the atmosphere remains reducing. To
analyze phosphine from the sorbent trap, it would be necessary to remove
a portion of the resin and chromatograph the contents directly. This can
be done in several ways but all involve significant difficulty and result
in poor detectability. This analysis would have to be performed on site
prior to extraction of the trap for organics. Phosphine will be lost under
normal conditions of handling and extraction of the XAD-2 resin.
The solubility of PH~ in water is very small and none is expected to
o
be found in the condensate. As mentioned above, phosphine is an effective
reducing agent and for this reason, it is expected to be found in the
first impinger trap. The reaction with H^CL will yield phosphorous and/or
phosphoric acid. The reaction would be quantitative if the impinger were
basic and for this reason a portion of the PH- may survive to be trapped
in the second impinger. Analysis of the impingers at this point would
only yield total phosphorus of all forms in the effluent stream and could
not be directly related to PH3 in the original gas stream.
Phosphine may be generated by the direct reaction of elemental phos-
phorus with hydrogen at elevated temperatures (>300°C), increased hydrogen
pressure tends to yield much greater quantities of the gas. A small
amount of diphosphine is often produced when PhL is generated, and is
pyrophoric. Phosphine is sparingly soluble in water and shows only a
slight tendency to produce the phosphonous ion (PH4)+. When the phosphonous
ion is formed it is very unstable and could not be determined in a "real"
sample.
AsH3 (Arsine) ~
Arsine is extremely poisonous and is readily decomposed by heat to
arsenic, which is deposited on hot surfaces as a metallic mirror. The
decomposition temperature of arsine to arsenic is reported to be 300°C,
44
-------
however in the presence of metal surfaces or impurities, the reaction can
take place at lower temperatures.
If any arsine were to survive passage through the probe, cyclones, and
filter its distribution should resemble that of phosphine. Problems of
analysis for arsine in the sorbent trap are also similar to those of
phosphine which have been previously discussed. Arsine is a more powerful
reducing agent than phosphine and would not be expected to exit the first
oxidative tmpinger. Any arsine which reaches the first impinger would be
converted to arsenous acid, a stable form of arsenic sutiable for analysis
by specialized atomic absorption techniques.
Arsine is not formed by direct reaction of arsenic with elemental
hydrogen since the temperatures required for this reaction cause decompo-
sition, however under conditions of very high hydrogen pressure, some arsine
may be formed. Arsine is most commonly formed by electrolytic reaction,
and may be detected in those industries where such processes occur and
arsenic is present. It has also been observed that specific strains of
bacteria or fungi can convert organoarsenic compounds to arsine at a level
harmful to animal life.
SbH3 (Stibine) —
The thermal instability of stibine will prevent its passage through
the probe. At 200°C stibine is very rapidly decomposed and will be deposited
as metallic antimony in the early stages of the train. Analysis for
stibine based on its chemistry using the SASS train for collection is
virtually impossible.
Due to its thermal instability stibine tends to be formed in those
processes where electrolytic or catalytic reactions are performed. Metal
refineries where water comes in contact with hot antimony containing
materials tend to produce stibine. Stibine is also generated during the
charging of batteries contaminated with antimony. Stibine decomposes even
at room temperature, so hazards associated with exposure are usually
related to close work or confined areas.
Organometallic Forms of P, As, and Sb --
In general, the organometallic forms of the elements are more stable
45
-------
than the hydrides. The degree of substitution (RMH2, R2MN or RgM where
H = P, As, or Sb) increases the boiling point of the compound and also the
amount of that compound which may be found in the sorbent trap. An
increase in the carbon number of the R group (i.e., -CH3, -C2H5. "^5)
also increases the boiling point of the compound. Analysis for the
organometallic forms is possible by GC and/or GC/MS from the XAD-2 resin
by direct volatilization, however the concentration of these materials is
expected to be very low and micro techniques for trapping may be required
for identification and quantisation. Analysis of the bulk of the sorbent
trap will generally yield no data on organometallic forms, due to the low
level of material expected to be present in most sources.
i
i
3.5.2 SASS Distribution of Reduced Sulfur Species j
The determination of reduced sulfur species after SASS train sampling
should be reasonably effective although quantitative results may be
somewhat difficult to obtain because of the distribution of the various
forms. After a reduced sulfur species enters the first oxidative impinger,
the identity of the parent compound is lost since similar products are
formed by oxidation of a number of starting species (see distribution
Figure 3-3). Specific cases are discussed below:
H£S (Hydrogen Sulfide) --
Hydrogen sulfide is a weakly acidic gas and can associate with basic
solid surfaces to only a slight degree. It is soluble in water by dissoci-
ation and the degree of solubility is pH dependent.
Ka = 9.1xlO"8
H2S(g) + H20 * — HS" + H30
Ka = 1.2x1 Of15
HS" + H20 * • - S" + H30*
Hydrogen sulfide is a mild reducing agent and in aqueous solution, on
exposure to light and atmospheric oxygen, will produce free sulfur by the
following reaction:
46
-------
PROBE
200-CMAX
100 30
CYCLONE CYCLONE
1
10
CYCLONE FILTER
COOLING
(20-Q
xAD-2
SO WE NT
H2S
COS
RSH
VL
L =
M =
H =
= Very small concentration
Small concentration
Moderate concentration
Large concentration
— —
1 L
J
«•> <•* /O*\
• L-M
CONDENSATE
H2°2
IMP1NGERS
2,31 M CS)M-H
M-H (pH Dependent)
FIGURE 3-3 Probable SASS Distribution of Reduced Sulfur Species
-------
h v
2H2S + 0 - *> 2H20 + 2S
Any Hydrogen sulfide in the probe, cyclones, and filter region will
be found adsorbed on basic substrates (e.g., flyash). The extent of this
adsorption will be limited by the temperature of this zone. Adsorbed
hydrogen sulfide can be determined by thermal desorption from the substrate
followed by GC analysis. The presence of oxidized species and water can
result in oxidation of the H2S and interfere with the proposed GC analysis
by reducing the hLS levels. The presence of oxidized materials however, is
unlikely in a reducing stream where HpS is expected to be found.
Some hydrogen sulfide may be present in the XAD-2 module. The
breakthrough volume for H2$ is rather small and only an equilibrium
concentration is likely to be present. Special precautions must be taken
to analyze for H2S present in the XAD-2 module. A portion of the polymer
must be thermally desorbed and the hLS passed to an analyzer (GC or other
specific detector). Standard handling techniques and solvent extraction
will result in the loss of any adsorbed HgS 1n the XAD-2 resin.
A significant concentration of H^S is expected in the condensate. The
solubility of HgS in water is pH dependent, therefore the more basic the
condensate, the greater its capacity for HgS. The condensate may be analyzed
by direct injection gas chromatography using flame photometric detection
(GC/FPD) or by acidifying the solution and purging with an inert gas prior
to analysis by GC/FPD.
Hydrogen sulfide which survives beyond the XAD-2 trap and condensate
module will be entrained in the first impinger. The reaction at this point
will produce an oxidized form of sulfur, sulfonic acid, S0,= , or SO-,= ,
O T1
depending on the nature of other materials present in the impinger. After
oxidation the H,,S will be indistinguishable from other forms of sulfur and
only total sulfur could be determined.
COS (Carbonyl Sulfide) —
Carbonyl sulfide is a reasonably stable gas which is readily analyzed
by several techniques including wet chemical, chroma tographic, and
48
-------
spectrophotometric. Very little COS will be found in the probe, cyclones
and filters. Some COS will be present in the XAD-2 trap, however analysis
of this sample will be difficult for the same reasons given for H S. The
major portion of the COS taken from an effluent stream using a SASS train
will be present in the condensate due to the solubility of COS in water.
This solubility is increased by the presence of organic matter and/or base.
A slow decomposition occurs in water, catalyzed by base according to the
following reaction:
OH"
COS . *. C03= + S=
Quantative analysis of the COS in the condensate requires rapid analysis
after sampling. The decomposition described above will cause errors in
both the COS and HgS analyses.
COS can be analyzed directly by GC/FPD with few interferences, or by
spectrophotometric techniques. Carbonyl sulfide can be trapped in a
ethanolic solution of piperdine producing piperdine monothiocarbamate
which has a. distinctive ultraviolet absorption spectrum. This method of
sampling will permit the determination of COS, CS2, and-thiophene in the
same sample.
COS which enters the impingers will be oxidized, producing CO, C02,
SO,", and SO,". Identification of the original structure will not be
possible after oxidation.
RSH (Organo Mercaptans) --
The distribution of mercaptans in the SASS train is dependent on
molecular weight, as it relates to volatility. Some relatively small
portion of the RSH compounds will be adsorbed on particulate matter. The
amount of RSH found in the XAD-2 module will vary according to volatility.
Highly volatile materials will pass the module with a minimal volume of
gas (low breakthrough volume) while the higher boiling mercaptans will
be more effectively entrained. GC/MS is a suitable technique for qualitative
Identification and quantitative determination of mercaptans from the XAD-2
module. Precautions must be taken in sample handling to minimize loss
especially of the more volatile components prior to analysis.
49
-------
Some RSH compounds are expected to be found in the condensate. Modi-
fication of the original compound structure is expected to be minimal, at
this point, and similar to that in the module.
RSH compounds which survive to reach the impingers will react in the
first impinger and in most cases no correlation with original structure
will be possible. Adsorption in a resin filled trap (XAD-2 or Tenax GC)
is probably the best method for sampling a complex series of mercaptans.
The trap should be followed by a basic impinger to entrain any materials
which pass the adsorption trap. An analysis of the material in the trap
by GC/MS or GC/FPD will permit direct qualitative and quantitative
determination.
3.5.3 SASS Distribution of Reduced Nitrogen Species (NH3» HCN, and (CN)o)
The reduced nitrogen compounds discussed in this section are generally
•
stable and therefore more readily sampled using the SASS train than some
of the other materials previously described. Analysis for specific reduced
nitrogen compounds requires special care and techniques for handling the
SASS train components to obtain good data on compound type and quantity
(see distribution Figure 3-4). The special care required is discussed with
respect to each individual compound below. It should be noted that the
toxicity of hydrogen cyanide (HCN) and cyanogen (CN)2 is very great.
Ammonia (NH,) —
Ammonia is a weakly basic gas and therefore its adsorption on acidic
substrates is minimal. The presence of water, either vapor or liquid, causes
a more basic reaction producing the NH4+ ion. Very little ammonia is
expected to be found in the probe, cyclones, or filter. Some ammonium salts
may be present but no determination of the original form could be made. A
small amount of ammonia may be present in the XAD-2 sorbent trap. The
breakthrough volume of the gas should be relatively small based on published
data of the performance of NH3 on Chromosorb 101 . Contact of NH3 gas with
water will result in effective entrainment and for this reason the highest
concentration of ammonia is expected in the condensate. The pH of the
condensate will dictate its total capacity for ammonia (the lesser the pH,
the greater the capacity) which will be present in the form of the MH4+ ion
50
-------
200°CMAX
1
PROBE
I
1
CYCLONE CYCLONE
•••*••
CYCLONE FILTER
COOLING
(20-Q
pL2l VL
(3) L-M
___ ___ ___ __ __ ^._ ___ ___ __ __ _„ __ J
CONDENSATE
CD NH3
(2) HCN
(D (CN)2
L = Small concentration
M - Medium concentration
H = Large concentration
11,2,31 H
XAD-2
SORIENT
1
1
ME
L
H2U2
IMP1NGERS
— APS
APS
FIGURE 3-4 Probable SASS Distribution for Reduced Nitrogen Species
-------
according to the following equilibrium:
Ka = 1.8xlO"5
NH3 + H20 M *~ NH4+ + OH"
Analysis for NH,, in the aqueous condensate will depend on concentration.
41
In a very clean system (low contamination of organic matter, etc.) an NH^ -
specific electrode could be used. For small concentrations, the water
sample can be analyzed by direct injection GC. For trace quantities, the
sample can be concentrated by raising the pH of the solution and purging to
trap the NH, on an adsorbent such as Tenax, or Chromosorb 103. Following
the concentration step, the sample can be analyzed by GC or GC/MS. Other
cleanup and concentration techniques can also be used as dictated by the
nature of interfering materials in the condensate.
Analysis for ammonia in the XAD-2 sorbent trap will be..more difficult
since the NH, will be lost if handled using the normal SASS train preparation
procedures. If NH- in the sorbent trap is to be analyzed, it can be recovered
directly by thermal desorption followed by GC analysis, or by extraction
with a mildly acidic aqueous solution.
Small quantities of NH3 may be present in the first impinger. The
mechanism for entrainment is based on solubility rather than oxidation.
Analysis of this impinger can be accomplished by neutralization and GC
separation. After long periods of standing the action of the peroxide
on ammonia will decrease the concentration by the production of N2 and HJD.
Hydrogen Cyanide (HCN) —
Hydrogen cyanide is a weak acid, highly stable, and very toxic. It
is missible with water in which it dissociates according to the equilibrium:
Ka = 2.1xlO~9
H20 + HCN ^ »-" CN~ + H30+
HCN is a liquid at room temperature and has a boiling point of 20°C. In
the liquid state it can polymerize violently in the absence of stabilizers.
The presence of moisture inhibits this polymerization.
The chemistry of HCN suggests that it will be found mainly in the
liquid condensate, dissociated according to its equilibrium, depending on
52
-------
the quantity of water in the condensate and the pH. Analysis of HCN can be
accomplished by GC using several gas-solid adsorbent columns. If the
condensate is very clean, the cyanide can be determined by ion specific
electrode techniques. A small amount of HCN is expected to be found in the
XAD-2 module. Analysis'of this portion of the train for HCN requires the
same precautions as outlined for ammonia. An XAD-2 trapped sample can be
recovered by extraction with mildly basic water. Only a small portion of
the HCN is expected to reach the impingers, where it would be lost due to
oxidation and conversion to volatile gaseous products.
Cyanogen (CNg) --
Cyanogen is a relatively stable gas at room temperature. Upon heating
(300-500°C) it can polymerize to form the ladder structure given below:
The polymer once produced is stable to about 850°C at which point it reverts
to (CN)2. Depending on the temperature of the sampled source and the probe
temperature gradient, a significant concentration of polymer can be formed
and will remain primarily in the probe. Some of this material may also be
found in the cycTones and filter, the location being dependent on particle
size.
If the polymerization does not occur or occurs only to a small extent,
the majority of the (CN)2 is expected to be ffiund in the condensate.
Cyanogen is soluble in water but decomposes slowly on standing according to
the following, base catalyzed reaction.
The ability to identify and quantitate cyanogen in the condensate
depends on the extent of its decomposition reaction which in turn depends
53
-------
on the time from sampling to analysis. Some cyanogen is expected to be
present in the XAD-2 trap and this analysis has the same limitations as
those described for NH3 and HCN above. The toxicity of (CN)2 is very
similar to the toxicity of HCN.
3.5.4 SASS Train Distribution for Mercury, Selenium and Metal Carbonyls
Volatile metals pose a special problem for the SASS train which is best
suited for organic species and participate material. Structure identification
for volatile metals will be almost impossible due to chemical modification
by the train and their expected small concentrations. The toxicity of
mercury as the metal is quite great as are most of its compounds. In the
case of selenium the metal is reported to possess little toxicity, whereas
its compounds are very toxic.
Mercury (Hg) —
The distribution of mercury in the SASS train (Figure 3-5) is dictated
mainly by its vapor pressure. Very little of the metal will remain in the
probe, cyclones, and filter. Some may exist as amalgams with other
metallic forms on the particulate matter collected in the cyclones and
filter. The major portion of the mercury will condense at the XAD-2 module
and be found in the condensate. Mercury h&s little affinity for XAD-2,
therefore, it would not be found in this portion of the SASS train unless
it is trapped in a low spot as a puddle. Mercury found in the condensate
should exist as the metal or be converted to the sulfide by the action of
H2S if it is present in the process stream. At this time, it is not clear
that an analysis for mercury metal will give accurate results. The
possibility of sulfide formation in the train will impose a significant
analysis error. The small amount of mercury which is likely to pass the
condensate region will be oxidized by the impinger solution and information
concerning its original structure on emission will be obscured.
Organomecurials, as governed by volatility, will be found in the
condensate region or in the impingers. If present in the condensate, the
organomercurials can be analyzed by GC/MS to determine their structure and
amount. Organomecurials which reach the impingers will be oxidized and
determination of their original structure will not be possible.
54
-------
200»CMAX
1
PROBE
3/1 I//
CYCLONE CYCLONE CYCLONE FILTER
COOLING
(20-O
H
L
Variable
en
en
CONOENSATE
Hg
Se
MCO
L = Small concentration
M » Medium concentration
H « Large concentration
XAD-2
SORKNT
1
1
-------
Selenium (Se) —
Selenium is not a particularly volatile metal (melting point =217 C
and boiling point =685°C) when compared to mercury (BP = 356°C). It is
expected that the majority of the metallic selenium will be in the flyash.
Selenium passing through the probe, cyclones, and filter will probably be
scrubbed by the XAD-2 module. This action would be the result of simple
filtration rather than physical adsorption. Selenium metal is not expected
to be found in the condensate or the impingers. Organoselenium compounds
and hydrogen selenide, if formed, will be distributed in much the same way
as described for mercury. Compound identification would also be virtually
impossible if these materials were sampled using the SASS train.
Metal Carbonyls (MCO) —
The SASS train is totally inadequate for the sampling of metal carbonyls,
The carbonyls will decompose in the probe, cyclones, or filter according to
their stability, yielding the metal and liberating carbon monoxide. The
more stable carbonyls may reach the impingers were they too will decompose.
Special sampling techniques are required for these materials, followed by
compound specific analysis.
56
-------
SECTION 4.0
SAMPLING AND ANALYSIS OF GASEOUS REDUCED INORGANIC COMPOUNDS
The sampling and analysis procedures presented in this section have
been identified from the open literature, developed or modified in the
laboratory, and in some cases tested during a field study on an actual
source of reduced inorganic emissions. The procedures are detailed and
and their application is limited to one or at most a few individual reduced
t
inorganic compounds. Due to the generally unstable nature of reduced
inorganic compounds, the procedures require specialized sampling equipment
and techniques. For the purpose of sampling and analysis, reduced inorganic
compounds can best be divided into groups based on their acidic, basic, or
neutral characteristics. Stability of the species to oxidation is also an
important parameter as illustrated by the metal hydrides (Section 4.3.1).
The species selected for determination in the acidic class include:
hydrogen sulfide, mercaptans, and hydrogen cyanide. The basic group
consists of ammonia and low molecular amines while the neutral class includes
metals, hydrides, cyanogen and carbonyl sulfide.
4.1 SAMPLING AND ANALYSIS OF ACIDIC REDUCED INORGANIC GASES
An understanding of the chemistry of specific compounds to be sampled
and analyzed is the first step in establishing methods or recommending
procedures. The chemistry of the stream, previously discussed in Section
2.0, from which a sample is taken may also influence methodology to be used.
Hydrogen sulfide is a weakly acidic gas and for this reason associates
will base substrates only to a slight degree. The presence of water,
however, causes a dissociation of the hydrogen sulfide molecule resulting
in water solubility, the degree to which is pH dependent. Hydrogen sulfide
is a mild reducing agent which on exposure to light and air in an aqueous
57
-------
solution will produce free sulfur. Sulfides of many metals are also formed
in aqueous solution most of which are insoluble. Care must be taken in the
design of sampling equipment to avoid hydrogen sulfide losses due to non-
recovered moisture fallout and metal sulfide formation.
Mercaptans behave similarly to hydrogen sulfide, however as the
molecular weight of the compound increases its organic character predominates.
Low molecular mercaptans are considered in this report as reduced inorganic
species but the techniques discussed will decrease in effectiveness as the
R group carbon numbers (RSH, R = CHg, C^Hg, CgHy, etc) are increased. Each
individual mercaptan must be considered separately as to sampling efficiency
and analysis accuracy. In addition, mercaptans react with metal surfaces
and are converted to the disulfide in the presence of air, under rather
mild conditions. For this reason extreme care in the design of sampling
equipment must be taken.
Hydrogen cyanide is quite similar to hydrogen sulfide in its gaseous
and solution characteristics. Like hydrogen sulfide, the solubility of
HCN in water is pH dependent. Additionally, HCN is thermally stable and
highly toxic both as the gas and in solution.
4.1.1 Sampling Techniques for Acidic Reduced Inorganic Gases
For the purpose of this discussion, sampling will be treated in terms
of sample collection, concentration, preservation and introduction to the
analysis technique.as an off-line batch process. The use of grab techniques
for high concentration species and/or on-site analysis will not be addressed
in detail. The techniques discussed were chosen to minimize sample contam-
ination, to facilitate sub-ppb determination, to provide for a degree of
preconcentration, and to allow for simplicity of application. For the
analytical results to be meaningful, sample integrity must be maintained.
To achieve this the sampling method must avoid fractionation, evaporation,
chemical reaction or biological degradation. It is obvious that the
sampling technique will have a great impact on the accuracy, reproducability,
limits of detection, and the credibility of analytical results.
Impinger Trapping Techniques for Acidic Reduced Inorganic Gases
Several impinger solutions were investigated during the course of this
58
-------
study to determine their ability to entrain acidic gases (i.e., H S, HCN,
and RSH). The results of these tests show the best impinger solution to
be basic cadmium sulfate. Original work on the use of basic cadmium
sulfate for trapping hydrogen sulfide was reported by O'Keefe and co-workers }.
Prior to the evaluation of sampling techniques, standards were obtained
(Scott Environmental - H2$ and C^SH and Matheson - HCN) of the acidic gases
to be analyzed. The hydrogen cyanide was obtained in a pure form while the
hydrogen sulfide and ethylmercaptan were obtained as dilute mixtures, 100
ppm and 110 ppm respectively, in helium. These standards were used to
evaluate the trapping efficiency of the impinger sampling system and to
provide samples for the development of analysis techniques.
The apparatus shown in Figure 4-1 was used to introduce pure reduced
inorganic gases into an Impinger train and to also introduce dilute gaseous
mixtures. Two impingers were used in series to obtain samples for sub-
sequent analysis.
During the evaluation phase, samples of a known volume of hydrogen
cyanide were slowly added to the Impinger train by introduction at the
Teflon^ tee (Figure 4-1). The results of the impinger train study are
present in Table 4-1. The general lack of detected species in the second
Impinger indicates good trapping effeciency however, if higher flow rates
are used the effeciency will probably decrease. Under these circumstances
3 or 4 impingers should be used in series to ensure efficient sample
recovery. The effect of interferences on trapping efficiency was not
evaluated, however no problems are expected unless the cadmium sulfate is
totally consumed during the sampling operation or the basic character of
the solution upset. An alternative method for hydrogen cyanide sampling
involves the use of concentrated sulfuric acid impingers. The technique
has been used successfully to determine HCN in shale oil conversion process
effluents (2). The method involves the use of dilute hydrochloric acid
Impingers to remove ammonia followed by concentrated sulfuric Impingers.
The concentrated sulfuric acid hydrolyzes the HCN to ammonia. The impinger
solution is then analyzed for ammonia by any of several analysis techniques,
some of which are discussed in Section 4.2.
59
-------
TEFLON TEE
WITH SEPTUM
FLOW
METER
VENT TO
HOOD
1/8 IN. OD
TEFLON TUBING
t
STANDARD
SAMPLE
MIXTURE
GLASS IMPINGERS FILLED WITH
1) BASIC CdSO4 - ACIDIC GAS TRAP1NG
2) DILUTE HCI - BASIC GAS TRAPING
HELIUM
FIGURE 4-1 Sample Preparation Apparatus for Evaluation of Implnger Solutions
-------
Table 4-1
Impinger Trapping Efficiency
Sample Amount added 1st. Impinger 2nd. Impinger
H,S 1 vg T ND
10 yg yes ND
100 yg yes ND
HCN 1W9 T ND
10 yg yes ND
100 yg yes T
WH 1V9 T Tn
25 10 wg -yes ND
100 yg yes T
61
-------
Solid Adsorbent Materials for Sampling Acidic Reduced Inorganic Gases —
The use of adsorbent materials for sampling acidic reduced inorganic
gases was evaluated using hydrogen sulfide since it 1s typically the first
compound to elute from most chromatographlc columns (I.e., lowest break
through volume). Initial studies were conducted using tenax GC and XAD-2.
Both of these materials were found to be Inadequate for the sampling of
H2S because of very low break through volumes even at reduced temperature
(0°C). One candidate material, Porapak QS, was found to be marginally
acceptable at 0°C. A complete evaluation of adsorbent sampling techniques
for H2S was not conducted since liquid filled implngers were found superior
for all of the compounds of interest. In addition the impingers provided
a more stable and transportable sample for off site analysis.
Grab Sampling for Acidic Reduced Inorganic Gases —
When field analytical equipment is available and the reduced inorganic
sample concentration in the effluent stream 1s relatively high, grab
sampling Is the prefered method. The rapid analysis in the field results
in less expense and the samples do not require significant stabilization.
When samples are taken for laboratory analysis, grab sampling techniques
are not recommended. Sample losses due to condensation, leakage, and
chemical modification of reactive compounds result in unreliable analytical
data. In most cases water vapor is condensed when a grab sample is taken
and the presence of water will significantly reduce the concentration of
acidic reduced inorganic gases in the vapor phase due to their inherent
water solubility. To reduce the effect of water vapor, an ice trap system
(see Figure 4-2) is often used. This sampling device will consistently
produce low results unless the condensate in the trap 1s analyzed together
with the gas bags.
4.1.2 Analysis Methods for Acidic Reduced Inorganic Gases
The chemical state of the sampled species often dictates the analysis
technique to be used. Impinger solutions, if relatively clean, can be
analyzed using ion specific electrodes or classical wet chemistry techniques.
For more complex mixtures, regeneration of the original sample gas is often
62
-------
FLOW
CONTROL
PROiE
CO
GLASS
WOOL
PUMP
EMPTY IMPINGER
TO REMOVE MOISTURE
FLOW
METER
TEOLAR
GRAB BAG
FIGURE 4-2 Typical Grab Gas Sampling System
-------
required to minimize Interference problems. For samples adsorbed on solid
substrates (adsorbent sampling), thermal desorbtlon or extraction with an
appropriate solvent may be used prior to analysis. Grab samples may be
analyzed directly or after concentration using a solid adsorbent or
cryogenic trapping.
The procedure to be used for analysis will be dependent on the matrix
from which the sample was taken, possible Interferences, and the sampling
technique. The following discussion presents techniques currently In use
as well as procedures developed as a part of this task.
Analysis of Implnger Solutions for Acidic Reduced Inorganic Gases —
In most cases where "real" effluent streams are sampled, direct
analysis of the Implnger solutions Is impossible due to the large number
of Interferences. For this reason, 1t was determined that the best
analytical approach was to develop methods 1n which the sample Is returned
to Its original state. In the case of acidic gases entrained in impinger
solution the samples would be regenerated and analyzed as a gas. In this
work the apparatus shown in Figure 4-3 was used for the regeneration of
acid gases prior to analysis. The procedure for regeneration involves
removing a representative aliquot of the Implnger solution (the impinger
may contain solids which must also be proportionally taken) and placing it
in the regeneration flask. A helium purge 1s begun (100-300 cc/min) and
the collection trap cooled. Acid (1M H2SO^) is added to the flask to
regenerate the gaseous acidic species and to reduce their water solubility.
The helium purge is continued for five minutes with mild heating to effectively
remove the sample gas.
Several techniques were studied for recovering the sample gas purged
from the impinger solutions, including trapping with dry ice/acetone, liquid
4f
nitrogen and solid adsorbents. The most efficient combination for sample
recovery proved to be a trap packed with Porapak QS and cooled using a dry
ice/acetone bath. The total purge gas volume should be kept to a minimum
to avoid sample break through and ice formation in the trap. When liquid
nitrogen was used to trap the sample gas, the Teflon® valves leaked during
the warming cycle apparently due to a significant Increase in pressure.
Drying of the purged gases using magnesium perchlorate or 5A molecular
64
-------
BURET FOR REAGENT ADDITION
HEATER
1/16 IN. OD
TEFLON TUBING
TEFLON
CONNECTORS
VALVE TRAP
COLD
BATH
1/16" OD x 12"
TEFLON TUUNG
3" SECTION PACKED
WITH PORAPAK OS
HELIUM
FIGURE 4-3 Regeneration Apparatus for Samples Obtained Using Implnger Sampling Techniques
-------
sieves tended to improve detectability, but further work must be done to
determine their effect on compound integrity and quantitative recovery from
a variety of samples.
Gaseous separation can be accomplished by either gas-solid or gas-
liquid chromatography. The most common packings for gas-solid chromatography
include silica gel, alumina, activated charcoal, molecular sieves, and
porous polymers. The molecular sieve and porous polymer substrates are
most often used. Care must be taken to avoid irreversable adsorption on
the solid phase packing which can result in reduced column performance and
low calculated recovery. As an example the adsorption of water on a molecular
sieve column significantly reduces its separation effeciency and the water
can only be removed by baking the column at elevated temperatures with a
gas purge.
Gas-liquid chromatography separation requires the gases under study
to have different solubilities in the liquid phase. If an approprate
column can be found for a specific analysis the resultant peaks tend to be
very s./metrical as opposed to the tailing peaks common to gas-solid
adsorbants. The disadvantage of liquid stationary phases include de-
composition by reactive gases resulting in sample loss and excessive
column bleed at the higher temperature typically required for analysis.
In most cases a general purpose liquid phase is unavailable for separation
of reduced inorganic gases.
Analyses of the acidic gases presented in this report were performed
using gas-solid chromatography with the conditions for analysis given
below:
Column Type: Glass 3M X 4mm i.d.
Column Packing: Porapak QS;80-100 mesh
p
Injector: 4 Port Teflon Valve System
Detector: Thermal Conductivity
Column Temperature: 25°C-120°C@ 8°C/min, after
a 10 minute hold at 25°C
After purging the sample from the impinger solution, the trap containing
the sample, (Figure 4-3) was heated to 100°C and injected onto the GC
column. A typical chromatogram for acidic as well as some neutral compounds is
66
-------
shown 1n Figure 4-4. Quantitatlon was achieved by calibration with
standard gases. Recovery for the various acidic gases studied using this
impinger technique is presented in Table 4-2. These results include
sampling as well as analysis recoveries. The higher recovery for ethyl
mercaptan is probably due to its lower affinity for water than the other
two species. The losses of HCN and H2$ are probably the result of water
condensation prior to the collection trap followed by dissolution of HCN
and H2S in the droplets.
Other techniques for the determination of HCN in aqueous solution
include the picrate colorimetric method (3), polarography (4,5), and
potentiometry with ion selective electrodes (6). Other methods for the
determination of H«S and mercaptans include titration of the sulflde and/or
mercaptide ion with Cd+
-------
CH3CH2SH
(CM),
ch
00
HCN
I
4
RETENTION TIME (MINUTES)
I
6
FIGURE 4-4 Typical Chromatogram for Reduced Inorganic Gases Using Porapak QS
-------
Table 4-2
Recovery of Add Gases From Implnger Solution
Sample Technique Recovery
HCN Acidify and 68 - 72%
purge
H?S Acidify and 71 - 79%
purge
C?H5SH Acidify and 81 - 86%
purge
69
-------
-J
o
ADSORBENT
TRAP
GRAB GAS
BAG
FLOW
MEASURING
DEVICE
TEFLON SAMPLE VALVE
TOGAS
CHROMATOGRAPH
1/8" OD TEFLON
TUBING
3" SECTION PACKED
WITH PORAPAK QS
FIGURE 4-5 Resin Adsorption Trap for Preconcentratlon of Solid Adsorbed or Grab Samples
-------
technique studied Involved removal of the sample from the resin by
extraction with a basic aqueous solution. Analysis of the resulting aqueous
solution can be accomplished in the same manner as previously discussed
for the implnger solutions. Low recoveries were experienced in all cases
when this procedure was attempted. The low recoveries were probably due
to excessive sample handling and inefficient removal of the acidic species
from the adsorbent.
Analysis of Grab Samples for Acidic Inorganic Gases --
Grab gas samples can be effectively analyzed on site using gas
chromatography techniques. The samples should be removed from the sampling
container by expulsion or purging and trapped on an adsorbent as previously
described (Figure 4-5). This technique allows for a rapid injection of the
sample into the gas chromatograph. The conditions to be used for the gas
chromatography are the same as those discussed above.
Interferences are a significant problem when grab samples are analyzed.
To minimize the effect of these interferences, selective GC detectors are
recommended. The flame photometric detector 1s quite sensitive to the
sulfur species being studied as well as COS and CS2- The nitrogen/phosphorous
(N/P) alkali flame detector is -very sensitive to HCN. Cyanogen also responds
on this detector but NHg does not. The use of selective detectors may be
required 1f the organic content of the grab sample is high and the impurity
peaks elute 1n the same retention window as the reduced species of Interest.
Significantly more expense and skill is involved with the application
selective detectors, especially in the field. For these reasons their use
should be limited. In most cases off-site analysis of complex samples is
recommended over sophistocated on-site analysis for cost effectiveness.
71
-------
Table 4-3
Summary of Gas Chromatography Procedures for HCN
Reference Column Column Oven Carrier Gas Detector Remarks
Temperature (°C) (ml/min)
11 3/16" X 6' Porapak Q 50 N2(75) FID
12 1/4" X 8' - 25% Triacetin 75 He(108) TCD
on Chromosorb P
13 1/4" X 12' - Porapak R 109 He^ TCD
14 5/16" X 7' - 20% 104 H?(160) TCD Column degraded
Polyethylene Glycol (PEG) by water
1500 on Chromosorb
(1) Flow rate not specified.
-------
4.2 SAMPLING AND ANALYSIS OF BASIC REDUCED INORGANIC GASES
Ammonia and low molecular weight amines are the only basic gaseous
species considered as a part of this study. Ammonia Is a weakly basic gas
and as such adsorbs on acidic substrates only to a small extent. The
presence of water however, either vapor or liquid, produces a more basic
reaction producing the NH4+ 1on by the following equilibrium.
Ka = 1.8 X 10"5
NH3 + H20 ^ *- NH4+ + OH"
Because of Its high solubility 1n water ammonia Is most often sampled by
entrainment 1n an acidic (HC1) Implnger and analyzed by titration or
by gas chromatography. Thermal conductivity detection 1s typically
used when amines and ammonia are analyzed by gas chromatography.
Other specific detectors such as thermionic (N/P) cannot be applied
since they do not respond to ammonia.
4.2.1 Sampling For Basic Reduced Inorganic Gases
The three sampling methods previously discussed; Implngers, adsorbents
and grab sampling, are also commonly used for ammonia and low molecular
weight amines. The best technique studied 1s the entrainment of ammonia
1n a Implnger containing dilute HC1. The direct adsorption techniques suffer
from Interferences and breakthrough at rather low sample volumes. Grab
samples suffer great losses of NH3 due to high water solubility. Conden-
sation of water In the grab sample container 1s common and for complete
analysis any condensate as well as the gas must be analyzed.
Implnger Sampling for Gaseous Amines —
A large number of Implnger solutions for the entrainment of basic
reduced Inorganic gases were investigated during the course of this study.
The most effective impinger solution proved to be a dilute solution of acid
In water. Ammonia and most low molecular weight amines have significant
water solubility and In an acidic solution protonate to form the ammonium
ion Increasing solubility. Figure 4-1 shows the test apparatus used for
73
-------
evaluation of implnger trapping efficiency for* ammonia and the low molecular
weight amines. Both ammonia and dimethylamine were used in the evaluation.
The results prove that,to the detection limit of the analysis technique,
both compounds are 100% retained in the first impinger solution. Problems
with the subsequent analysis of ammonia and dimethylamine after impinger
sampling are discussed in Section 4.2.2. A field test of the impinger
sampling technique was conducted at the Paraho 011 Shale Demonstration
Plant.
Solid Adsorbent Materials for Sampling Basic Reduced Inorganic Gases —
The use of solid adsorbent materials for the sampling of basic reduced
inorganic gases was evaluated using ammonia as the model compound since it
typically has the lowest retention volume of the basic species to be
analyzed. As a result of these tests, Chromosorb 103 was identified as a
tentative candidate for the trapping of low molecular weight amines.
Although Chromosorb 103 was found to be best, the breakthrough volume is
rather low and temperatures of 0°C are required to achieve reasonable sample
size. If the concentration of ammonia in the effluent gas stream is high,
the solid adsorbent technique provides a convenient means of sampling,
however when the ammonia concentration is low adsorbent sampling is totally
Inadequate. For these reasons further tests using adsorbents was suspended
since impinger sampling proved to be much superior over a broad range of
sources and effluent concentrations.
Grab Sampling for Basic Reduced Inorganic Gases —
Grab sampling is the obvious preferred method when the analysis of samples
In the field is required. This technique 1s effective in sampling most
inorganic gases when the concentration in the effluent stream is relatively
high. The difficulty with sampling for ammonia by this technique stems from
its high solubility In water, which typically condenses in the grab sampling
container. Sample losses due to this effect can be extremely high if the
water vapor is not removed from the grab container by washing prior to
analysis.
74
-------
4-2-2 Analysis of Implnger Solutions for Basic Reduced Inorganic Gases
Attempts to remove ammonia from acidic aqueous Implnger solutions by
first making the solutions basic then purging with an Inert gas proved to
be inadequate. The recovery apparatus previously discussed and shown 1n
Figure 4-3 (Section 4.1.2) was initially tested for the removal of ammonia
from impinger solutions. The procedure used involved making the implnger
solution basic (1 M HaOH) and purging with helium while the solution was
being heated to about 100°C. The evolved ammonia was to be trapped in a
Chromosorb 103 filled tube cooled in an ice bath (0°C). When the trap was
allowed to warm to room temperature and its contents analyzed using gas
chromatography no ammonia was detected. Careful examimation of the trap
tubing revealed small droplets of water which had condensed between the
purging vessel and the Chromosorb 103 trap. It was assumed, add later
proved that the ammonia was being retained in the water droplets.
When the trap and connecting tubing was heated to 100°C before
Injection onto the gas chromatographic column, a 63% ammonia recovery was
obtained. Attempts to remove the water after the sample was purged from
the regeneration apparatus but before the Chromosorb 103 trap using various
adsorbents proved to decrease the total amount of ammonia recovered. When
calcium sulfate was tested for water removal the ammonia recovery fell to
15%. The use of 5A molecular sieves, preconditioned at 350°C under a
helium purge, provided a 62% ammonia recovery. Another precolumn, previously
reported (15) to remove water from ammonia before analysis, is barium oxide.
This material was not evaluated to determine ammonia recovery due to lack
of availability.
Because of the problems associated with trapping ammonia in the conven-
tional manner, a modified approach was attempted. Using the same regenerat-
ion flask shown in Figure 4-3, an aliquot of the acidic implnger solution
was neutralized with sodium hydroxide. The heating mantel was then placed
around the flask to heat the contents to boiling while nitrogen was purged
through the solution. Ammonia and water vapors were condensed into an ice
cooled microtrap (Figure 4-6) until approximately 250 microliters of
condensate were collected. If 25 milliters of impinger solution are used
1n the regeneration flask an effective concentration factor of 100 to 1 is
achieved. A portion of this condensate 1s then analyzed using gas chroma*
75
-------
•TEFLON CAP
-J
CTl
1/16" OD TEFLOh
TUBE
J
c
ICI
_c
MM
•M
mm
^m
«M
MM
:E
L
•••
•Mi
•MB
^H
i^
••i
tA
/ .
L?
^ j
TH
__ — 250 MICR
VENT TO HOOD
FIGURE 4-6 Ammonia Distillation Collector for Implnger Trapped Samples
-------
tographic procedures. Using this stream distillation technique, 88% recovery
for ammonia was obtained. Using the same technique, 97% of dimethylamine
was recovered.
When a stream with relatively few impurities is sampled, the impinger
solution can be analyzed for ammonia by direct titration, however when
other basic materials are present in the effluent stream, which is most
commonly the case, analysis of the ammonia is best accomplished using
gas chromatography. Several columns were evaluated for the determination
of ammonia, some of which are given in Table 4-4. The best column both in
terms of convience as well as performance was found to be Chromosorb 103.
This packing elutes ammonia and most low molecular weight amines without
excessive tailing, and water does not effect the column material or
interfere with the analysis of ammonia. The results reported for ammonia
recovery as a part of this report were obtained using Chromosorb 103 and
a micro-thermoconductivity detector. Thermoconductivity detectors are
only moderately sensitive and very low concentrations of ammonia cannot
be determined. Very few GC detectors have a good response for ammonia
and none of these are in wide spread.
Analysis of Solid Adsorbent Obtained Samples for Basic Reduced Inorganic
Gases --
If an adsorbent material is used to collect the basic inorganic gases,
it is best analyzed directly using gas chromatography and thermoconductivity
detection, as previously discussed. This approach will undoubtedly result
in GC peak broadening however it is expected that the concentration will
be relatively high if solid adsorbent sampling techniques were used. In
application^ small adsorbent trap is used for sampling. After a known
amount of the effluent stream has been sampled, the trap is connected to
the front of the gas chromatographic column. The helium flow is started
and the column programmed in temperature normally- It is expected that
this technique will result in low recoveries due to losses during sample
handling and irreproducable results due to inaccurate measurement of the
ammonia peak area.
Analysis of Grab Samples for Basic Reduced Inorganic Gases —
Because of the moisture condensation problem previously discussed
77
-------
Table 4-4
Effectiveness of Columns for Amlne Analysts
Column
Dlglycerol + 5% TEP on Chrom W
Chromosorb 103 Porous Polymer
2% TEP on Graphite
4% Carbowax 20 M + 0.8% KOH on
Carbopack B
3% Poly-A103 on Gas Chrom Q
Penwalt 223 on glass beads
10% Amlne 220 + 10% KOH on
Chromosorb W
Porapak Q treated with KOH
Porapak Q + 10% TEPA
Comments
Did not separate DMA from TMA at yg
concentration. Excessive bleed.
Separates most amines and NH, without
tailing, water does not Interfere.
Poor resolution.
Good but requires care in Its use.
Poor resolution.
Some tailing.
Effective at all concentrations.
Column good but requires care in use
Column good but requires care in use
78
-------
(Section 4.2.1) and the subsequent loss of ammonia by solution 1n this
condensed vapor, grab sample analysis can prove very difficult. The best
technique, If grab samples are required, is to purge the grab sample into
a mildly acidic impinger and then wash the interior portion of the grab
container with a mild acid and add this washing to the Impinger contents.
The analysis for ammonia is then accomplished using the same procedures as
outlined for impinger solution analysis above. It is not recommended that
grab samples be used for the determination of basic reduced inorganic gases
due to the obvious losses inherent with the technique.
Field Verification of The Impinger Sampling Procedure for Ammonia —
The field verification sampling for ammonia was conducted at the Paraho
Shale Oil Demonstration Plant. The samples were taken using four impingers
in series. The first impinger contained 20 ml of distilled water. The
second and third impingers contained 5% HC1 and the fourth contained silica
gel to dry the gas stream. The analysis for ammonia collected using this
impinger system was accomplished by titration (22), due to the high ammonia
concentration and lack of interferences. The results of the test are given
in Table 4-5. The ammonia levels were expectantly high from the conversion
process. The sampling points and a descreption of the plant are given in
Section 4.3.1. The samples exhibited good reproductabillty and show that
the level of ammonia varies with time.
79
-------
Table 4-5
Ammonia Analysis Results from Paraho Shale 011 Facility
Date Test Volume,of Gas NH_ Detected
(M3) 3(PPM)
9/77 NH3-1 .06 13,000
9/77 NH3-2 .05 18,000
9/77 NH3-3 .02 15,000
10/77 NH3-1 .08 5,000
10/77 NH3-2 .08 7,000
10/77 NH3-3 .09 6,000
10/77 NH3-4 .08 7,000
80
-------
4.3 SAMPLING AND ANALYSIS OF "NEUTRAL" REDUCED INORGANIC GASES
The term "neutral" reduced Inorganic gases is used for those species
which show little affinity to accept or denote a H+ in aqueous solution.
The sampling and analysis of these species is based on molecular character-
istics other than their affinity for acids or bases. Such compounds as
(CN)2, COS and AsH3 exhibit these characteristics as well as metals such
as mercury and selenium.
In most cases the elements and compounds studied are unstable and
must be sampled 1n a way that chemically alters their structure to provide
inhanced stability. As will be discussed below, this inherent reactivity
is used in most cases as the basis for sampling and analysis. General
purpose sampling equipment is for the most part not applicable to these
compounds and specialized sampling and analysis techniques must be used
to effect quantitative determination at low concentrations.
4.3.1 Sampling and Analysis of Selected Metal Hydrides (PHg. AsH3 and SbH3)
The methods discussed in this section are designed to sample and analyze
for arsenic in Its reduced forms such as arsine, methylarsine, and other
organometallic arsine compounds. In addition, stiblne and its organometalUc
forms and phosphine and its organometalHc forms can be determined. The
method 1s designed to provide for sampling of these gaseous species at the
trace level and to perform analysis remote from the emission source.
Traditional methods for the determination of the metals include atomic
absorption and spark source mass spectrometry, however these techniques
only determine total metal and do not determine the type of compounds in
which they may be found.
The sampling and analysis of reactive gases at low levels is a
challange, without instrumentation at the source. The trapping of gases
for remote analysis generally results In significant compound modification.
Armed with these facts, the methods presented here take advantage of the
chemistry of the compounds. The gases are chemically modified for stability
and then transported to the laboratory for analysis. All reduced compounds
of arsenic, antimony, and phosphorus are determined in a single sampling
thereby lowering the cost for both sampling and analysis.
81
-------
Previous work by Braman and co-workers (16,17) has resulted In procedures
for the determination arsenic oxidation states. Braman's techniques involve ,
the reduction of arsenic compounds using sodium borohydrlde at specific
solution pH resulting 1n their sequential gaseous evolution. The arsenic
oxidation states are determined by the pH at which the reduction and subsequent
evolution takes place. The reduction chemistry of Braman's method is shown
in Figure 4-7. The pH of the solution in which the reduction takes place
is very important since the various arsenic acids must be in their completely
protonated state before reduction can proceed. As an example; arsenous acid
(pKa = 9.23) can be reduced at a pH of 4-5. At this pH arsenic acid (pKa = 2.35)
will not be reduced and arsenic (III) can be determined 1n the presence of
arsenic (V). After the arsenic (III) is evolved the solution pH can be
lowered and the arsenic (V) reduced and determined. Braman used the
difference in boiling points of the organoarsenic compounds to provide for
their separation and determination. It has been suggested that antimony
compounds could be determined in much the same way (17).
The hydrides (phosphine, arsine, and stibine) can be formed in several
commercial processes, such as in a reducing acidic atmosphere where the
element 1s present (e.g., coal gasification or liquifaction) and by several
electrolytic processes. The stability of the hydrides 1s marginal decreasing
in the order PH3 > AsH3 » SbH3> so that stibine is very unstable, thermally
decomposing instantly to the metal under mild heat or even at room temper-
ature in only a few hours. Sampling techniques for the hydrides which
take advantage of their strong reducing character were investigated as
candidate methods. The expected low concentration of these compounds in
a typical source emission dictates micro techniques be used so that
subsequent analysis can be performed without excessive preconcentratlon.
The following discussion presents the chemistry of the hydrides as well as
sampling and analysis procedures developed for their determination.
Chemistry of Selected Hydrides (PH3> AsHg, and SbHj —
PH3 (Phosphine)
Phosphine, the most stable of the hydrides discussed, is not spontaneously
flammable but is readily oxidized by air upon ignition. The compound is
exceedingly poisonous, sparingly soluble 1n water, and 1s a strong reducing
82
-------
00
CO
O OH
ARSENIC ACID % / NaCNBH, NaBH,
pKa, - 2.25 As 3 O-As-OH 4 AsH.
P 1 / \ pH 1-2 (PARTIALLY) PH 1-2 3
ARSENOUSACID O-As-OH NaBH
9.23 p
METHYLARSONIC ACID
IV'"Dtl4 CH3A$H2 b.p. 2»C
DIMETHYLARSONIC ACID H3^ x-°
oKa * 6.19 As
CH/ \OH pH ,-2
O
PHENYLARSONIC ACID c.H. - As^ OH NaBH^
pK.,-3.59 6 pH,J C6H5A,H2 b.p. 148»C
FIGURE 4-7 Reduction Chemistry of Arsenic Adds
-------
agent.
Phosphlne is generated by the direct reaction of elemental phosphorus
with hydrogen at elevated temperatures (>300°C), increased pressure of
hydrogen tends to yield much greater quantites of the gas. Diphosphine is
often produced at a low level when PH3 is generated, and is pyrophoric.
Phosphine is sparingly soluble in water and shows only a slight tendency
to produce the phosphonous ion PH4+. When formed it is very unstable and
could not be determined in a "real" sample.
AsH3 (Arsine)
Arsine is extremely poisonous and is readily decomposed thermally to
arsenic metal, which is deposited on hot surfaces as a minor. The
decomposition temperature of arsine to arsenic is quoted to be 300°C.
However in the presence of metal surfaces or impurities, the reaction can
take place at much lower temperatures. Arsine is a more powerful reducing
agent than phosphine and is converted on oxidation to arsenous acid in
aqueous solution or arsenic trioxide in air.
Arsine is not formed by direct reaction of arsenic metal with elemental
hydrogen since the temperatures required for this reaction cause decompo-
sition. Under conditions of high hydrogen pressure, or by catalysis arsine
can be formed. Arsine is, however,formed by electrolytic reaction and
in those industries where such processes occur and arsenic is present arsine
may be evolved. It has also been observed that specific strains of bacteria
or fungi can convert organoarsenic compounds to arsine at a level which is
harmful to animal life.
SbH3 (Stibine)
Stibine has a high degree of thermal instability, at 200° C stibine is
very rapidly decomposed and will be deposited as metallic antimony. Due
to its thermal instability stibine tends to be formed in those processes
where electrolytic or catalytic reactions are performed. Metal refineries
where water comes in contact with hot antimony containing materials
(aluminum catalyzes this reaction) tend to produce stibine. It is also
generated when batteries contaminated with antimony are charged. Stibine
decomposes even at room temperature, so hazards associated with exposure
are usually related to close work or confined areas.
84
-------
Sampling for The Hydrides —
Due to the strong reducing nature of compounds such as phosphlne,
arslne, and stlblne, 1t was determined that an oxldatlve 1mp1nger would be
the best means for sampling the materials 1n a gaseous stream. Immediately
on contact with a strong (or even mild) oxldlzer, the hydrides react. In
an aqueous solution the hydrides are converted to their respective acids
(e.g., arslne 1s converted to a mixture of arsenous and arsenic adds).
Some assumptions must be made before this sampling technique 1s used. The
most Important of these 1s that the stream being sampled 1s Indeed reducing.
The assumption of a reducing stream must be made since the oxidized forms
of the elements will be determined as their respective reduced forms by
this procedure.
The sampling method recommended as a result of this work, utilizes
an oxldatlve Implnger train containing 30% hydrogen peroxide. The gases
from the reduced stream are pulled through the implngers using a small
vacuum pump until a volume consistent with detection requirements, has been
sampled.
Blanks are very Important for the subsequent analysis. Depending on
the type of detection system used, artifacts from the reagents used can
adversly affect results. By analyzing blanks these Interferences will at
least be noted and In most cases can be removed.
Under laboratory conditions, more than 90% of the arslne generated 1n
a reaction vessel can be trapped 1n a single midget Implnger filled with
30% H2(L. Less than 2% of the generated arslne appears 1n a second Implnger
connected In series. Some arslne probably remains 1n the reaction vessel
or decomposes 1n transit to the first Implnger.
Analysis of The Hydrides —
The method developed for the determination of the hydrides (PH3, AsH3,
and SbH3) requires, the use of GC/MS for separation and determination. The
procedure, as described, was verified In the laboratory using standards
prior to a field evaluation.
Samples obtained using the hydrogen peroxide Implngers previously
discussed must first be treated to destroy the HgO^ The destruction
85
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procedure Involves making the peroxide solution basic and refluxlng for
1 to 2 hours. The peroxide destruction 1s necessary since the subsequent
analysis requires reduction of the arsenic compounds In this 1mp1nger
solution. The degree of dlstructlon of the hydrogen peroxide can be
measured by taking a small amount of the sample and adding 1t to a solution
of potassium Iodide. If the solution remains colorless, the peroxide
destruction 1s complete. If the solution yellows, the destruction Is
Incomplete and a judgement has to be made as to whether the solution should
be refluxed longer or more reducing reagent added when the analysis 1s
performed.
Figure 4-8 shows the reduced gas generation apparatus which was used
for generating the hydride sample gas. For analysis, the sample Is allquoted
Into the generation cell, shown at the left of Figure 4-8. An excess of
oxalic add Is added to reduce the solution pH followed by sodium borohydrlde.
The system 1s purged with helium and the gas passed through a Drierite
trap to remove moisture. Moisture removal 1s required to avoid plugging
of the liquid nitrogen trap with 1ce. The sample Is condensed by the LN2
and the trap Isolated after reduction and purging 1s complete.
All connecting lines to the GC/MS must be non-metallic to avoid sample
degradation. The presence of any metal In the system will result In very
low recovery for the hydrides. It was necessary for this technique to
work, to remove the GC Injector block and connect the trap directly to the
glass column in the gas chromatograph. Once generated, the reduced gases
are stable for 1 to 3 hours. If analysis is performed during this period,
no significant sample degradation was observed. Samples allowed to stand
overnight after being reduced to their gaseous forms, even in the Inert
helium atmosphere used to purge the generation cell, decompose completely
to their respective metals. After generation, the sample trap is allowed
to warm, the valves opened, and the gaseous sample injected by flushing
with carrier gas onto the GC column.
During the initial phases of this work, the mass spectrometer was
scanned over a mass range which allowed for the determination of .all the
compounds of interest. Subsequent analysis have been accomplished with
higher sensitivity by monitoring narrow ranges of the mass spectrum where
the molecular Ions of the species of Interest predominate. The chromatography
86
-------
03
SAMPLE OR REAGENT
INTRODUCTION PORT
TRAP
GCCOl
t
.UMN
-a
*•».*•• r^
TC DETECTOR
OR MASS SPEC
FIGURE 4-8 Reduced Gas Evolution Apparatus
-------
was accomplished using a Carbowax column and the conditions given below:
• Column type: glass, 10% Carbowax 20M on Chromosorb 101, 100/120
mesh.
• Column length: 1 meter X 2 mm I.D.
• Flow rate: 20 cc/min (helium)
• Temperature program: 50°C for 1.5 min, 50°C - 100°C at 6°C/min
• No Injector was used for these analysis and the sample loop was
allowed to warm to room temperature (5 min) before analysis.
For less volatile organometallics, the loop was gently heated.
Figure 4-9 shows a reconstructed gas chromatogram of a mixture of
phosphine, arsine, stibine, and methylarslne. This chromatogram resulted
from a synthetic mixture produced by dissolving phosphoric acid, antimony
trioxide, arsenous acid, and methylarsenoic acid in water and reducing using
the procedure previously described. As can be seen the chromatography
allows for the separation of all components. The only interference occurs
with the coelution of phosphine and air. Figure 4-10 Illustrates this
coelution by displaying the molecular ion of phosphine (M/e « 34), plotted
on the same scale as the molecular ion for oxygen (M/e = 32), relative to
scan number. This interference was significant and could prohibit the
determination of phosphine on this GC column. Other work has shown that
this interference can be eliminated by using a 4A molecular sieve column
for the specific determination of phosphine. Figure 4-11 shows the spectrum
of phosphine with the interference from air being quite obvious.
Also on the Carbowax column, stibine coelutes with water, the amount
of water in the sample is a direct function of the age of the Drierite
used in the trap during the regeneration process. It was found that the
coelution of stibine and water did not adversely effect the determination
of stibine even at low concentrations. Figure 4-12 shows the spectrum of
stibine with its molecular ion at M/e = 124 and its antimony isotope pattern.
Arsine elutes in a very clean region of the chromatogram with no interferences,
The spectrum for arsine is shown for reference 1n Figure 4-13 and has a
molecular ion at mass 78. Arsine is monolsotopic and therefor has no
isotope pattern. Arsine shows only trival fragmentation with the loss of
hydrogen from the molecular ion as the main fragmentation process. Finally
the mass spectrum of methylarslne, molecular weight 92, is given in Figure
4-14 showing it to be similar to arsine except that the loss of methane is
-------
GAS CHROMATOGRAM
SAMPLE: 0.1 ML OF GAS
SAMPLE RUN: AS PAS
CALIB. RUN: C91
SCANS 1 TO 500
RELATIVE
INTENSITY
00
VO
SCAN
TIME
50
1:40
100
3:20
FIGURE 4-9 Resconstructed Gas Chromatogram of The
Hydrides Produced by Reduction Procedure
-------
M/E = 32
to
o
= 34
SCAN
TIME
-
PH3
_«A^
1 T i 1 | I | | 1 | 1 I | | | 1 1 I 1 | 1 1 1 1 | 1 1 1 1 | I 1 1 1 | I i I 1 | 1 i 1 1 | ! 1 | I
50 100 150 200 250 300 350 400 450 500
1:40 3s20 5:00 6:40 8:20 10:00 11:40 13:20 15:00 16:40
FIGURE 4-10 Mass Chromatograms for Oxygen (M/e=32)
and Phosphlne (M/e=34) Showing Coelutlon
-------
100.0
50.0
-
.1
1 1
MM
PH3
AIR
^^^ PH3
Ll I.I .. i
1 1 ' 1 * 1 i i i i i I i i i 1 | 1 i 1 i 1 i l i 1 i i i 1 i i i i
b 50 100 150 200
INT 62080.
FIGURE 4-11 Mass Spectrum of Phosphlne and A1r (Scan 22)
-------
VO
ro
100.0
50.0
H2°
T T ' 1 r I i I i I i I i I ' I i I i I ' I
M/E 50 100
124 Mf
SbH
3 .
INT 56320.
I ' I
150
FIGURE 4-12 Mass Spectrum of St1b1ne (Scan 325)
-------
100.0
vo
50.0 -
M/E
Ill 1 ' - - ' ' '' f - * *
Iii1!1! i I ' 1 ( I i
XAsH-
o
! I 1 i 1
I NT 31968.
20 30 40 50 60 70 80 90 100
FIGURE 4-13 Mass Spectrum of Arslne (Scan 128)
-------
100.0
50.0
M/E
n I
I ' I
ii.i
ill..
50
M/e = 92Mf .
CH AsH
INT 5184.
100
FIGURE 4-14 Mass Spectrum of Methyl Arslne (Scan 454)
-------
observed from the molecular Ion.
Figure 4-15 shows the mass spectrometer response to arsine as a function
of concentration 1n order to determine the linearity of the Instrument to
this reduced gas. The curve was generated by adding known amounts of
arsenous acid to the previously described reduction vessel and producing
known accounts of arsine. As can be seen, the response 1s linear from about
50 nanograms of arsine Injected to about 500 nanograms. A knowledge of the
linear response range permits the analyst to adjust the amount of material
in the generation vessel by using smaller or larger allquots of the sample.
Similarity, the response for stibine Is shown 1n Figure 4-16 with essentially
the same linear working region. Analysis should be performed only within
this linear region and the curve should be generated for each mass spectrometer
system used since the linear response of each instrument will be different.
The use of a mass spectrometer as a detector for this analysis can
only be described as "overkill". Less expensive systems need to be
investigated. A second draw back to the 6C/MS system is that the metallic
hydrides decompose in the mass spectrometer ion source producing conductive
paths. These conductive paths cause the mass spectrometer to become non-
functional in a very short period of time and Increase the frequency of
ion source cleaning.
As a part of this program the use of alternative detectors has been
studied. A thermoconductivity detector (TC) is a good general purpose GC
detector which responds to the hydrides. The TC detector however, lacks
sufficient sensitivity and specificity to be useful. The thermionic detector
(N/P) was evaluated as a possible alternative to mass spectrometry however
it was found not to respond to any of the hydrides, including ammonia. A
third detection system (not evaluated) is flame photometric detection. It
is anticipated that with the use of selective filters this detector may
prove to be the most practical. The flame photometric detector has the
inherent sensitivity and with proper filters should also have good selectivity.
It is doubtful that one could devise a flame photometric detection system
which would allow for complete analysis of all hydrides in one chromatographic
run since filter selection would be based on a specific element. Other
possible detection systems include micro wave discharge, spectral emission
and atomic absorption but the higher costs of these systems makes them less
95
-------
1440
1200
to
O
Q.
to
960
720
ID
O>
480
240
A$H3 RESPONSE VS. CONCENTRATION
USING NoBH4 REDUCTION PROCEDURE
AND GC/MS FINISH
200
400 600 800
CONC. NG ARSINE
1000
1200
FIGURE 4-15 Arslne Calibration Curve
-------
180
150
120
LU
ts>
Z
o
90
60
30
RESPONSE VS. CONCENTRATION USING
NaBH4 REDUCTION PROCEDURE AND GC/MS
FINISH
200 400 600 800
CONCENTRATION NG STIBINE
1000
1200
FIGURE 4-16 Stibine Calibration Curve
-------
practical.
Field Verification of Hydride Procedures —
A field test of the sampling and analysis procedures for the hydrides
was conducted at the Paraho Shale Oil Demonstration Plant. The Paraho
semiworks retort uses the same system configuration for solid and gas
handling as a full-scale plant. The retort is capable of being operated
in either a direct or indirect heating mode at mass feed rates of up to
200 Kg/hr/M2.
During the period of this test the retort was operated in the direct
mode (gas combustion) only. In this mode of operation the carbon on the
retorted shale is burned in the combustion zone (see Figure 4-17) to
provide the principle fuel for the process. The low calorie retort gases
are recycled to both the combustion zone and the gas preheating zone. The
portion of retort gas which is not recycled is sent to a thermal oxidizer
for combustion.
In operation, raw shale is fed into the top of the retort and passed
downward by gravity successively through a mist formation and preheating
zone, a retorting zone, a combustion zone, and finally, a residue cooling
and gas preheating zone. It is discharged through a hydraulically-operated
grate, which controls the discharge rate and maintains even flow across
the retort.
The oil vapors produced in the retorting zone are cooled to a stable
mist by the incoming raw shale (which is thereby preheated), and exit the
retort for collection. This mist is sent to a condenser, and finally a wet
electrostatic precipitator, for oil separation.
Samples for arsine were taken from the recycle gas stream at a point
between the electrostatic precipitator and the recycle gas blower (point
A, Figure 4-17). This location was chosen because of the moderate pressure
and temperature of the recycle gas. The moderate conditions allowed the
sample to be drawn through the impingers without treatment since the gas
is relatively free of oil mist.
The sample was drawn through 5 impingers in series. The first impinger
was empty, impingers 2-4 contained 100 ml of 30% H202, and the last impinger
contained 200 g of silica gel. The Impinger solutions were combined in
98
-------
vo
GRATE SPEED
CONTROLLER
RAM
SHALE
FORMATION
AND
PREHEATING
RETORTING
ZONE
COMBUSTION
ZONE
RESIDUE
COOLING AND
GAS
PREHEATING
OIL
i
rrf
PRODUCT
GAS
t
Wd
ELECTROSTATIC
PRECIPITATOR
T
OIL
GAS RECYCLE
BLOWER
AIR BLOWER
RETORTED SHALE
FIGURE 4-17 Schematic of Paraho Retort
-------
the field prior to transport to the laboratory for analysis.
A total of four Individual samples were obtained from the recycle gas
stream. These samples were analyzed In triplicate using the procedures
previously described.
The results of the analyses are presented 1n Table 4-6.
Table 4-6
I
Field Test Results for Arslne
3
Sample Volume Amount yg/M
No. Sampled Arslne Arslne
Detected
1 0.15 M3 .025 yg 0.17
2 0.14 M3 .035 yg 0.25
3 0.13 M3 .045 yg 0.35
4 0.13 M3 .060 yg 0.46
Arslne was the only hydride detected in the samples analyzed and no
organometallic species were detected. The results of triplicate analysis
of the same sample were within - 20% relative. The deviation of the amount
of arslne found between samples Is probably due to the small sample volumes
obtained and the non-homogeneity of the recycle gas stream due to process
variations.
4.3.2 Sampling and Analysis of The Volatile Elements (Hg and Se)
Volatile elements present special problems in sampling and analysis.
The most significant of these problems 1s the difficulty in determining
the exact structure of the compound or element emitted from a given source.
Most analytical procedures have the ability to determine the amount of an
element in a given stream but to state that 1t was emitted as the element
or the oxide is very difficult. The following sections give some insight
to this problem and suggests procedures to overcome the difficulty.
Sampling and Analysis For Mercury (Hg) —
Mercury is a health hazard due to absorption of nearly 80% of the
inhaled vapor by the body at concentrations between 50 and 350 yg/M3.
Elemental and organic mercury compounds pose additional problems by being
100
-------
absorbed through the skin. The toxicity of mercury 1s due to the strong
bonds formed by 1t with sulfur atoms In body components which results in
an interference in the various body functions including synthesis and
function of both enzymes and proteins. Mercury is a cumulative poison and
concentrates in the brain, liver, and other organs.
Mercury and tts compounds, are quite prominent environmental pollutants
from natural and manmade sources. Elemental mercury enters the atmosphere
from such sources as active geothermal sites, ore deposits, mining operations,
coal burning, and smelting operations. The most common forms of mercury
in the environment include the metal, halides, oxides and organomercurials.
Atomic absorption spectrometry (AAS) is the most common analytical
technique for the determination of mercury. In ideal cases it 1s capable
of determining elemental mercury at concentrations as low as 15 ng/M3
(18). The basic problem with AAS is its inability to distinguish the
form in which the mercury is present. Until recently, no techniques were
available for the specific determination of mercury compounds. The work
of Braman and Johnson (19,20) has recently established a method for species
identification of mercury and mercury compounds. The procedure utilizes
sequential, selective absorption tubes for separation of specific mercury
oxidation states and uses a DC discharge spectral emission detector for
analysis. Using this method, analysis can be performed accurately on
mercury concentrations as low as 0.1-0.5 ng/M of air samples as small as
0.1 M3.
In the procedure described by Braman, air samples are drawn through
a connected series of 10 cm quartz tubes containing selective absorbents
for the various chemical compounds of mercury. The first component of the
sample collection apparatus is a glass fiber filter (Gelman Instrument Co.
Type A) to retain particulate mercury. The volatile mercury species that
pass this filter are collected in the quartz tubes that are shown in
Figure 4-18. Also given in the figure is the function of each absorbant.
The components of this selective sampling device are connected with 1.0 cm
Teflon R sections. A1r samples are drawn through the absorption tubes at
about 1.5 1/min using a small diaphragm vacuum pump. Small quantities
of water from air saturation are reported not to interfer, but corrections
are required for temperature and the partial pressure of water in accordance
101
-------
PROBE SAMPLE IN
TYPE A GLASS FIBER FILTER
(RETAINS PARTICULATE Hg)
I
45-60 MESH CHROMOSORB W
SILICONIZED (5% W/W SE-30
METHYL SI LI CONE) TREATED WITH
HCI VAPOR. (RETAINS Hg (II)
COMPOUNDS, I.E., HgC)2)
45-60 MESH CHROMOSORB W
TREATED WITH NaOH. (RETAINS
METHYLMERCURY (II) COMPOUNDS)
45-60 MESH GLASS BEADS,
SILVERED (RETAINS Hg°)
60-80 MESH GLASS BEADS, GOLD
PLATED (RETAINS Dl METHYLMERCURY)
VENT
PUMP
FIGURE 4-18 The Function of Selective Absorbers for The Sampling of Gaseous Mercury Compounds
-------
with the standard ASTM test D 3195-73. The steps involved in the preparation
of the substrates for each of the absorption tubes is presented in Tables
4-7 to 4-10.
As can be seen from the description of the Braman sampling device the
separation of mercury compounds is achieved during the sampling process.
In addition the samples collected in this manner are stabilized for transport
to an off-site laboratory. The actual analysis of the mercury content of
the selective absorption tubes can be accomplished by any of several tech-
niques. The use of a DC discharge systems offers high sensitivity at modest
cost, however AAS, electrochemical, or wet chemical techniques may also
be used with various levels of sensitivity.
After air sampling is complete the sampling tubes are disassembled,
sealed and sent to the laboratory. Once received they are treated to
remove mercury or mercury compounds for analysis. If the DC discharge system
is to be used the particulate filter is placed without handling directly
into an empty Pyrex tube, of similar size to the sampling tubes. A heating
coil is placed around the tube and it is attached directly to the DC discharge
detector. After air is removed by passage of He carrier gas, the discharge
is initiated and the tube heated rapidly to 550°C. Mercury compounds on the
particulate filter are detected as a single peak during thermal desorption.
No determination of compound type is possible in this portion of the sampling
system. The Chromosorb W(HC1) and Chromosorb W(NaOH) absorption tubes are
treated in a similar manner. The Chromosorb W(HC1) tube is heated to 250°C
to remove the mercury (II) compounds (e.g., HgClg) and the Chromosorb W(NaOH)
tube is heated to 300°C to remove the methyl mercury type compounds. All
tubes must be blanked prior to use.
Calibration is made by using saturated mercury metal vapor in air.
A gas-tight 0-0.5 ml syringe is used to sample the mercury vapor above a
metal pool in a test tube fitted with a rubber septum. The test tube is
kept in a water bath at room temperature measured to -1°C. Vapor pressure
data are used to calculate the amount of mercury in the air delivered from
the syringe.
This procedure was exaustively investigated by the authors and appears
to be developed to the point that additional study is not required. With
reasonable care, the method can analyze for mercury compounds as well as
103
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Table 4-7
Preparation of Siliconlzed Chromosorb W (HC1)
For Mercury Sampling
t Pack 10-cm quartz tube to a length
of 7 cm with Chromosorb W, 45-60 mesh.
• Add 60-70 milligrams of SE-30 to
the top of the packed tube.
t Initiate a flow of helium
carrier gas through tube.
t Slowly heat the tube with a wire coil heater
until the SE-30 melts and is distributed onto
Chromosorb W.
• Excess silicone is removed by heating the column
for 10-20 min at 300°C with flow.
• Treat the Chromosorb W filled tube with lOcc of HC1
vapors taken from the headspace of a bottle of
concentrated HC1.
t Repeat HC1 treatment after 8-10 uses.
104
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Table 4-8
Preparation of NaOH Treated Chromosorb W
For Mercury Sampling
Pack a 10 cm quartz tube to a 6-7 cm
depth with Chromosorb W (45-60 mesh).
Wet the Chromosorb W with 0.05N
sodium hydroxide.
Dry the material by passing
carrier gas through column.
Discard after failure during use.
105
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Table 4-9
Preparation of Silvered Glass Beads
For Mercury Sampling
t Place 45-60 mesh glass beads 1n a
container.
• Silver coat using the silver nitrate,
ammonia, and formaldehyde silvering
technique.
t Inspect peads under a microscope to determine
that at least 90% are silvered (silver should
be about 14% by weight on the beads).
106
-------
Table 4-10
Preparation of Gold Coated Glass Beads
For Mercury Sampling
Dissolve 12 grams of gold metal
1n aqua regla.
Add concentrated HC1 to remove the nitrates and
convert the dissolved gold to auric chloride.
Add 50 grams of HC1 washed 45-60
mesh glass beads.
Slowly evaporate, while stirring the auric
chloride-glass bead mixture, to near dryness.
Pack the semi sol id mass Into a 10 cm quartz tube,
pass He or N£ carrier gas through the tube and heat
with a tube furnace.
Add \\2 gas through a "T" in the carrier gas
line as the tube Is heated.
After extended use heat the tube to 550-600°C
while passing air to remove carbon or si 11 cone
deposits.
107
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the metal in air at concentrations approaching 0.5 ng/M . The Braman
approach should be considered as a standard sampling procedure when
mercury compound identification from an emission source is required.
Sampling and Analysis for Selenium (Se) —
The levels of selenium and its compounds are of considerable interest
as environmental pollutants. This interest is due to the toxic and
potentially carcinogenic properties of selenium. Its natural abundance
as well as the wide use of selenium or its compounds in manufacturing and
industrial application, necessitate effective methods for measuring this
element, especially at trace levels. Selenium can be found in many forms
in the environment, including the metal, halides, oxides and organometallics.
Possible sources of trace selenium include natural fuels, leather
goods, cloth materials, paper and other wood products. Coal has been found
with as much as 7.4 ppm Se and significant amounts have been found in
newsprint. The principal means of access to the environment is by incin-
erator stack emission where concentrations of 2 yg/M have been determined.
Atomic absorption spectrometry (AAS) is the accepted analytical
technique for the determination of selenium. In Ideal cases the AAS is
capable of determining elemental selenium at concentrations as low as 2 yg/M
based on a 30 M sample. The basic problem with AAS is its inability to
distinguish the form in which the selenium is present.
Sampling of effluent gas streams for selenium may be accomplished by
the use of oxidative implngers such as H202 or absorbent filter paper wetted
with strong cyanide solution. The purposed all glass sampling apparatus
for selenium consists of a sampling probe through which the sample gas 1s
drawn followed by a filter (recommended is the Gelman Instrument Co. Type
glass fiber filter). The filter may either be placed in the filter holder
directly or treated with cyanide solution before use. The criteria for
using the filter with or without cyanide impregnation 1s based on particulate
loading of the stream to be sampled. In the case of high particulate loading
the filter should be used untreated to better handle the particulate catch.
In actual use, gas samples are pumped through a system of three implngers
in series which are cooled by an ice bath. The first and second impingers
108
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contain 750 milliters of a 30% hydrogen peroxide solution and the third
contains silica gel to protect the pump and dry test meter from moisture
and possible reagent carry over. The recommended sampling apparatus 1s
shown in Figure 4-19. After gas sampling 1s complete the filter is placed
in a sealed petrl dish aftd the impinger solutions are transferred into
Nalgene bottles for return to the laboratory for analysis.
Selenium 1s determined in the samples by graphite furnace atomlzation
AAS. The H202 implnger samples are treated with nickel nitrate solution
until a concentration of 1% nickel is achieved. The nickel nitrate Is used
to convert the selenium to the selenide form during ashing in the graphite
furnace. In this form the response for selenium 1s inhanced.
Particulate samples and filters are first digested using an HF-HN03
acid solution, then nickel nitrate is added to achieve a 12 solution prior
to analysis by AAS. When the above techniques are used no compound identi-
fication is possible. At the present time no procedure appears adequate
for compound identification of low selenium concentrations in effluent
samples.
4.3.3 Sampling and Analysis of Miscellaneous Reduced Inorganic Gases
Two of the reduced gaseous Inorganic compounds studied cannot be
readily classified; these are cyanogen, (CN)2, and carbonyl sulfide, COS.
Cyanogen is very toxic (toxicity similar to HCN) and relatively stable at
room temperature. At elevated temperature the compound tends to poly-
merize when maintained in the gaseous state. Carbonyl sulfide is also
highly toxic and stable at room temperature. Carbonyl sulfide is soluble
in water where it slowly decomposes to form carbonate and sulfide.
Sampling and analysis for COS and (CN)2 1s typically more conventional
than some of the other reduced inorganic gases because of stability.
Impinger and adsorbent sampling techniques hold the most promise for simple
and rapid identification of the species. Gas chromatography 1s applicable
for separation and analysis for both COS and (CN)2«
Sampling for Carbonyl Sulfide and Cyanogen —
The traditional sampling procedure (21) for carbonyl sulfide Involves
109
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SAMPLING
PROW
FILTER
HOLDER
BY-PASS
VALVE
VACUUM
GAUGE
30%
MAIN
VALVE
AIR-TIGHT
PUMP
FIGURE 4-19 All Glass Sampling Apparatus for Selenium
-------
the use of an Impinger train containing calcium chloride and ammonium
hydroxide for the selective removal of COS. Figure 4-20 illustrates this
impinger train which was used for a field verification of the method. The
first two impingers contain aqueous Cd(OH)2 to remove H2S which will
interfere with the determination of COS if present. The third impinger
is filled with an aqueous solution of CaCl2 and NH4OH for the removal of
COS. The fourth Impinger contains a KOH/alcohol solution for the selective
removal of CS2.
This sampling system is inexpensive to assemble and use and provides
an accurate measure of COS in effluents which are relatively clean. If
the source to be sampled has a significant particulate level a filter
should precede the first impinger to avoid plugging of the impinger frit.
The sampling for (CN)2 1s based on the ability of aqueous base to
hydrolyze cyanogen to cyanide (CN~) and cyanate (OCN~). For laboratory
tests the (CN)2 was passed through two Impingers in series containing
0.1 M NaOH to determine the effeciency of (CNL removal. The results show
only a trace quantity of (CN)2 in the second Impinger suggesting adequate
scrubbing of the gas stream using a single impinger. These experiments
were conducted on an ideal gas stream and for field use at least two
impingers in series should be used.
Adsorbent trap sampling techniques of COS and (CN)2 were also evaluated
as a part of this program. The procedures and trapping media tested have
been previously discussed in Section 4.1. Although the adsorbent techniques
met with some success the breakthrough volumes for COS and (CN)2 were low
enough that trace level determination in real effluent samples would not
be possible. The best adsorbent trap studied proved to be the Porapak QS
system previously described.
Analysis of Carbonyl Sulfide and Cyanogen —
The analysis of the impinger traps for carbonyl sulflde and carbon
disulfide was accomplished by oxidation of the impinger solution using
hydrogen peroxide (H202) to form sulfate (S04=) from the entrained sample.
A barium salt is added to the product solution and the sulfate determined
as barium sulfate gravimetrically. The entire test can be conducted in the
field or shipped to an off-site laboratory. The results of a field
m
-------
PROK
PUMP
Cd(OH)2
SOLUTION
Cd(OH).
7.5% CaCI,
SOLUTION 1% NH4OH
SOLUTION
H2S
REMOVAL
COS
REMOVAL
KOH
ALCOHOL
cs2
REMOVAL
FIGURE 4-20 Implnger Sampling System for COS and CS,
-------
verification test of this procedure are given in Table 4-11. The results
and observation of the test suggests that H2S interference may still be a
significant problem. Further work must be done to fully evaluate this
procedure before it is routinely applied to all sources of COS.
The analysis of cyanogen collected using the basic Impingers discussed
above was accomplished by a modified Werner procedure. The modified
Werner method for the determination of cyanate depends on the formation
of a blue copper-pyridine-cyanate complex which is extracted from an
aqueous solution with chloroform. The modified method is the result of
selecting an optimum addition of pyridine and copper sulfate solution for
the test. Color intensity is reduced by extreme conditions of pH, but
a change of buffer pH from 5.0 to 8.0 caused only a 5% loss in sensitivity.
A pH slightly above 6, using the cacodylate buffer, was selected since
gradual decomposition of cyanate can occur at or below pH 5.5. Color
stability is excellent over extended periods, if evaporation of chloroform
is prevented.
The cyanate determination was performed directly 1n the 0.1 M NaOH
impinger solution. The basic impinger solution may also contain S~, CN~,
and RS~ Ions, all of which are candidates for interferences in the OCN"
determination. These possible interferences may be delt with simply by
determining the OCN" after the evolution of the aforementioned species
by acidification and helium purging. No field tests were conducted using
this procedure and possible interferences have not been fully evaluated,
however the acidification step prior to the cyanate determination should
remove many of the potential interferences sbch as HCN and H2$.
The analysis of adsorbent trapped samples is conducted as previously
discussed in Section 4.1. The analysis by gas chromatography using selective
detectors (i.e., thermionic (N/P) alkali flame for (CN)2 and flame photometric
for H?S) provides for clean chromatograms and reproducable results. The
errors which are associated with the adsorbent sampling techniques signifi-
cantly over shadow the analytical finish. The ease of analysis associated
with adsorption trapped samples leads one to hope for future developments
in the area of selective adsorbents for specific reduced inorganic compounds.
If this is accomplished full utilization of the recently developed highly
specific and sensitive gas chromatographic detectors can realized.
113
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Table 4-11
Field Verification Results of Samples Taken at The Paraho Oil
Shale Demonstration Facility
Sample Volume of ? Concentration Concentration
A1r Sampled (FT) COS (ppm) CS2 (ppm)
13 18
ND ] ND ]
20 ND ]
9/6-1
9/6-2
9/6-3
0.013
0.022
0.022
1 ND • Not Detected
714
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Where approprate concentrations are suspected, grab sampling
techniques can be employed. The techniques for both grab sampling and
analysis have been discussed 1n detail (Section 4.1) and are applicable
to (CN)2 and COS when care 1s exercised.
115
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SECTION 5.0
SUGGESTIONS FOR FURTHER RESEARCH
A description is provided in this report of the methodology for the
sampling and analysis of representative reduced inorganic compounds from a
variety of sources. Further research is required before the proposed
methodology can be routinely used in the field. Some of the additional
research required includes:
• Evaluate complex samples for interferences.
• Determination of the recovery of all reduced species in mixtures
described fay a statistical matrix.
• Determination of the storage life of samples collected, i.e.,
impinger and adsorbent trapped samples.
• Complete characterization of Porapak QS and other specialized
materials for use 1n adsorbent traps for selective compound
sampling.
• Design and evaluation of cartridge-type adsorbent traps that can
be stored for extended periods before and after use without
changes in efficiency for sampling or degradation of trapped
samples.
• Establish conditions to permit rapid sampling and analysis of
higher molecular weight amines and mercaptans.
• Choose from existing sources or design selective detectors for
the identification and determination of reduced inorganic species,
• Improve or design new on-site monitors for reduced inorganic
species in effluent streams.
The sampling and analysis of reduced inorganic species is a very
116
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important area of study. Very few current environmental assessment
programs are using compound specific techniques for sampling and analysis.
Therefore little information is being gained on the true risk associated
with a given source.
117
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REFERENCES
1. O'Keefe, A.F., G.C. Ortman; Anal,/ Chem., 38(1966).
2. TRW Draft Final Report, Sampling and Analysis for Retort and Combustion
Gases at The Paraho Shale Oil Demonstration Plant, IERL, EPA, Cinn, OH.
Jan. 1978.
3. Reilly, D.A.; Anal. Chem., 49, 322(1977).
4. Humphrey, R.E., S.W. Sharp; Anal. Chem., 48, 222(1976).
5. Canterford, D.R.; Anal. Chem., 47_, 88(1975).
6. Black, M., R.P. Herbst, D.R. Hitchcock; Anal. Chem., 50, 848(1978).
7. Eshman, D.L.; Anal. Chem., 48, 918(1976).
8. Gutknecht, W.F.; Anal. Chem., 47_, 2316(1975).
9. Manoulchehr, Y., R.L. Birke; Anal. Chem., 49, 1380(1977).
10. Moore, W.M., V.F. Gaylor; Anal. Chem., 49_, 1386(1977).
11. Claeys, R.R. and Freund, H., Environmental Science and Technology, 2^,
458(1968).
12. Isbell, R.E., Anal. Chem. 35_, 255(1963).
13. Voorhoeve, R.J.H., Patel, C.K.N., Trimbel, I.E. and Kerl, R.J., Science,
190, 149(1975).
14. Woolmington K.G., Journal of Applied Chemistry, 11, 114(1961).
15. Grob, K., Zurcher, F., J. Chromatog., 117, 285(1976).
16. Braman, R.S., Justen, L.L., Foreback, C.C., Anal. Chem., 44, 1476-1479
(1972).
17. Braman, R.S., Justen, L.L., Foreback, C.C., Anal. Chem., 40, 95(1968).
18. Long, S.J., Scott, D.R., Thompson, R.J., Anal. Chem., 45_, 2227(1973).
19. Braman, R.S., Johnson, D.L., Environ, Sci. Technol., V2, 996(1974).
20. Johnson, D.L., Braman, R.S., Environ, Sci. Techno!., 1_2, 1003(1974).
118
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21. Jacobs, M.B., The Chemical Analysis of Air Pollutants, 162.(1960),
22. Air Pollution Control District, Country of Los Angeles, Source
Testing. Manual 5th. Ed. (1972).
119
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TECHNICAL REPORT DATA
(Please read Inunctions on the reverse beforecompletinel
I EPA-600/2-79-199
EPA/IERL-RTP Procedures Manual: Level 2 Sampling
and Analysis of Selected Reduced Inorganic Compounds
R.G.Beimer, H.E. Green, and J.R.Denson
J9. PERFORMING ORGANIZATION NAME AND ADDRESS "
TRW Defense and Space Systems Group
One Space Park
Redondo Beach, California 90278
112. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
3. RECIPIENT'S ACCESSION NO.
6. REPORT DATE
November 1979
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
INE624
11. CONTRACT/GRANT NO.
68-02-2165, Task 103
13. TYPE OF REPORT AND PERIOD COVERED
Task Final; 10/76 - 6/79
14. SPONSORING AGENCY CODE
EPA/600/13
15. SUPPLEMENTARY NOTES ffiRL-RTP project officer is Frank E. Briden, Mail Drop 62, 919/
541-2557.
The report describes Level 2 sampling and analysis procedures for deter-
[mining emission rates of specific reduced inorganic compounds, including metal and
non-metal hydrides, sulfides, carbonyls, and elements. For the report, a reduced
inorganic compound is a metal or non-metal that is bound to hydrogen (in its zero
valence state) or to carbon. It includes a literature review identifying (1) industries
where reduced inorganic compounds are likely to be found, and (2) sampling and
analysis methods previously used to identify and quantitate inorganic compounds.
The literature review identifies sampling methods that have been applied to reduced
inorganic compounds and analysis techniques that can identify compound structure,
rather than just total elemental emissions. The procedures given in the report are
detailed and, for the most part, specific to individual compounds. Accuracy, inter-
ferences , and detection limits have been determined for manyof the species under
laboratory conditions. Some of the procedures were tested as part of a field study
at a shale oil conversion plant.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Croup
[Pollution Carbonyl Compounds
[Inorganic Compounds
Reduction (Chemistry)
Sampling Elements
Analyzing
Hydrides
|18. DISTRIBUTION STATEMENT
Release to Public
Pollution Control
Stationary Sources
Sulfides
19. SECURITY CLASS (This Report)
Unclassified
20. SECURITY CLASS (This page)
Unclassified
13B 07C
07B
14B
21. NO. OF PAGES
122.
22. PRICE
EPA Form 2220-1 (9-73)
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