APPLICABILITY OF INORGANIC SOLIDS OTHER THAN
OXIDES TO THE DEVELOPMENT OF NEW PROCESSES
FOR REMOVING S00 FROM FLUE GASES
Final Phase I Report
Contract PH-22-68-57
CHEMICAL RESEARCH AND DEVELOPMENT CENTER
FMC CORPORATION
PRINCETON, NEW JERSEY
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APPLICABILITY OF INORGANIC SOLIDS OTHER THAN
OXIDES TO THE DEVELOPMENT OF NEW PROCESSES
FOR REMOVING S02 FROM FLUE GASES
Final Phase I Report
Contract PH-22-68-57
for
New Process Development Section
Division of Process Control Engineering Program
National Air Pollution Control Administration
Public Health Service
U. S. Department of Health, Education and Welfare
FMC Corporation
Chemical Research and Development Center
Central Research Department
June, 1969
PCR-684
i
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CONTENTS
INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . .
SCOPE OF WORK. . . . . . . . . . . . . . . . . . . . . . . . .
CONCLUSIONS. . . . . . . . . . . . . . . . . . . . . . . . . .
RECOMMENDATIONS
. . .
. . . .
. . .
. . . . .
.........
SECTION I
ACKNOWLEDGEMENTS. . .
. . . . .
SECTION II
SECTION III
. . .
. . . . .
. . . .
. . .
. . . . . .
INFORMATION SEARCH AND STORAGE.
. . . .
A.
B.
C.
D.
PURPOSE. . . . . . . . . . . . . . . . . . . . . . . .
SOURCES SEARCHED. . . . . . . . . . . . . . . . . . . .
SCOPE OF THE SEARCH. . . . . . . . . . . . . . . . . .
REFERENCE CODE SYSTEMS. . . . . . . . . . . . . . . .
1. McBee Card Coding System. . . . . . . . . . . . .
2. Computer Coding System. . . . . . . . . . . . . .
a. Reference Type. . . . . ... . . . . . . . . .
b. Material Class. . . . . . . . . . . . . . . .
c. Elements and Element Combinations. . . . . . .
d. Additional Descriptors. . . . . . . . . . . .
3. Computer Input. . . . . . . . . . . . . . . . . . .
a. Citation Input. . . . . . . . . . . . . . . .
b. Code Input. . . . . . . . . . . . . . . . . .
4. Function of Computer Programs. . . . . . . . . . .
EVALUATION AND DISCUSSION OF THE RESULTS OF
THE LITERATURE SURVEY. . . . . . . . . . . . . .
A.
B.
C.
D.
E.
F.
G.
H.
1.
Clays. . . . . . . . . . . . . . . . . . . . . . . . .
Mineral Products. . ... . . . . . . . . . . . . . . .
Industrial Waste. . . . . . . . . . . . . . . . . . .
Inorganic Salts. . . . . . . . . . . . . . . . . . .
Metals and Alloys. . . . . . . . . . . . . . . . . . .
Covalent Compounds. . . . . . . . . . . . . . . . . .
Non-Metallic Elements. . . . . . . . . . . . . . . . .
Oxides of Non-Metals. . . . . . . . . . . . . . . . .
Hydroxides. . . . . . . . . . . . . . . . . . . . . .
REVIEW OF SOLID-GAS CONTACTORS .
. . .
. . . . .
A.
Carbon Based Processes
1. Reinluft Process
2. Sulfacid Process
3. Hitachi Process
. . . . . . . . . . . . . . . . 42
. . . . . . . . . . . . . . . . . .45
. . . . . . . . . . . . . . . . . 46
. . . . . . . . . . . . . . . . . 47
Page
1
4
6
7
8
9
9
9
9
13
13
17
17
19
19
19
24
24
27
27
29
29
30
31
32
34
35
36
38
40
42
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APPENDIX II -
~
I
SECTION IV
SECTION V
APPENDIX I
CONTENTS (Cont'd)
B.
Non-Carbon Processes. . . . . . . . . . . . . . . . .
1. Grillo Process. . . . . . . . . . . . . . . . . .
2. Still Process. . . . . . . . . . . . . . . . . .
Comparison of Existing Processes. . . . . . . . . . .
New Developments. . . . . . . . . .' . . . . . . . . .
Process Economics. . . . . . . . . . . . . . . . . .
C.
D.
E.
THERMODYNAMICS OF SULFUR DIOXIDE SORPTION
. . .
BIBLIOGRAPHY.
. . . .
. . .
. . . . .
. . . . .
PROCESS REVIEWS
. . .
. . . . .
. . .
. . . . .
THERMODYNAMIC COMPUTATIONS. .
. . .
. . . . . .
APPENDIX III - COMPUTER PROGRAMS
. . . . .
. . .0 . .
. . . . .
Page
47
47
48
49
52
56
59
67
112
129
172
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I
II
III
IV
V
VI
VII
VIII
IX
X
XI
XII
XIII
XIV
XV
l.
2.
LIST OF TABLES
Sources Consulted in the Literature Search on S02
Removal from Flue Gas. . . . . . . . . . . . . . . . . .
Reference Code System for McBee Card Punching.
. . . . .
Reference Type Codes
. . . . .
. . . . . . . . . .
Computer Code For Generic Material Classes for S02
Removal from Flue Gas. . . . . . . . . . . . . . .
Computer Code for Elements and Element Combinations
Elements Included Under More Than One Computer Code
Lis t i ng .....................
Additional Computer Descriptors. . .
Sample Reference Sheet as Keypunched
. . . .
. . .
. . .
. . .
. . .
. . . . . .
. . .
. . . .
Carbon Regeneration Reactions Having Favorable Log K
. . .
Comparison of Present Iporganic Solid Sorption Processes
Sources of Thermodynamic Data for Metal Salts.
. . . . .
Standard Metal Compound Reaction Classes. . . . .
Minimum Values of Kp for Thermodynamic Feasibility
Accepting S02 From Power Plant Stack Gas. . . . .
Minimum LoglOKp's for Reaction Classes VII and VIII
. . . .
. . .
. . .
Range of Thermodynamic Feasibility of Various Reactions.
LIST OF FIGURES
Sample McBee Card.
SO Removal Process
x .
. . . . .
. . . .
. . .
. . . .
. . .
. . . .
. . . .
. . . .
. . .
. . . .
Page
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15
18
20
21
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26
37
50
60
61
62
63
65
14
55
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INTRODUCTION
The magnitude of problems associated with pollution control
has commanded considerable attention during the last few years.
The Federal Government currently is engaged in a,program to
develop acceptable methods to control emissions from stationary
air pollution sources. Until now the discharge of pollutants
into the atmosphere has been a common practice. Now these
discharges have reached such proportions that emission control
has become a matter of considerable concern. Major gaseous
contributors to atmospheric pollution are hydrocarbons, carbon
monoxide, nitrogen oxides, and sulfur oxides from the combustion
of fossil fuels and hydrocarbons.
The emission of sulfur oxides into the atmosphere is
increasing rapidly and in many areas has already reached serious
proportions. In large concentrations, sulfur dioxide is toxic.
In lower concentrations it acts an an irritant to the respiratory
tract, and prolonged exposure to as little as ten parts per million
can be harmful to the elderly and those suffering from lung or
circulatory diseases. Vegetation is especially sensitive to
sulfur dioxide, and certain plants have been observed to show the
effects of sulfur dioxide poisoning in atmospheres containing
less than one part per million of sulfur dioxide. Sulfur dioxide
and its oxidation product, sulfuric acid, are the principal causes
of acidity in rain water and fog; and the acid is one of the major
pollutants in mine drainage waters. The harmful effects of
sulfur dioxide include corrosion of ferrous and non-ferrous metals,
and deterioration of materials and fabrics, such as wool, cotton
and leather. .
The U.S. Public Health Service has estimated that 21 million
tons of sulfur dioxide are released annually to the atmosphere in
the United States from the combustion of coal and fuel oil (400).
About 85% of this results from the combustion of coal containing
from 0.5 to more than 5% of sulfur. The remaining 15% comes from
the combustion of fuel oils containing less than 5% of sulfur.
The fraction of sulfur in the fuel that is converted to sulfur
dioxide depends on the type of fuel burnt and the method of firing
used. Thus, in stoker firing of coal, 60% to 75% of the sulfur is
converted to sulfur dioxide, whereas over 95% of the sulfur in
coal is oxidized to sulfur dioxide in pulverized fuel firing.
With oil firing, virtually all the sulfur is released as sulfur
dioxide. :.
The largest source of sulfur oxide emission is stationery
power generation plants (388, 389) which release about 46% of all
sulfur oxides emitted to the atmosphere. An additional 32% comes
from industrial, commercial, and miscellaneous combustion operations;
12% from the smelting of ores; and 10% from combined industrial
sources, which include sulfuric acid manufacturing, pulp and paper
mills, chemical plants, refuse incineration, oil refining, and
coke processing. Combustion of fuel oil and coal in power plant
installations generally produces flue gases containing from 0.05%
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to 0.35% of sulfur dioxide. Some smelting opetations produce flue
gases having as much as 6% to 8% sulfur oxid~s. The latter streams
can be partially cleaned by scrubbing solutions, such as aqueous
ammonia or aluminum sulphate, and various amine solutions. The
scrubbed gases often contain more S02 than power plant flue gases.
The pollution caused by smelters, contact acid plants, and refineries
is small compared to that caused by power plants and is, in most
instances, concentrated in only a few localities. On the other
hand, pollution caused "by power plant installations is widespread.
An effective clean-up of this gas with its relatively low S02
content has not been achieved economically to date.
It has been estimated that the electric power generating
capacity of this country in 1980 will be more than double that
existing in 1965. A substantial portion of this projected growth
is expected to be provided by nuclear fuel power plants which emit
no sulfur oxides. The majority of the remainder of the growth
will be provided by fossil fuel plants. For example, projections
show that coal use for power" generation is expected to increase
from 272 million tons inl967 to 440 million tons in 1980 - with
allowance for an optimistic growth rate of nuclear power. If
such growth in electric generating capacity occurs, effective
measures will have to be taken to reduce the quantity of S02
emitted to the atmosphere or the pollution problem will be seriously
aggravated in the near future.
There are two major ways to limit pollution by sulfur dioxide
from fossil fuels. The" sulfur can either be removed from the fuel
prior to combustion, or the sulfur dioxide can be removed from the
products of combustion. The use of low sulfur fuels is not feasible.
The United States does not have adequate supplies of low sulfur
coal for use in power generation plants, and. most of the available
low sulfur coal is located in areas far removed from the major
power-generating areas.
Oil desulfurization, usually via hydrogenation, is expensive
and may, in some cases, make-the cost of the desulfurizedfuel
prohibitive for power plant generation.
To cope with the problems relating to pollution from combustion
sources, the NAPCAis sponsoring a series of programs aimed at
studying processes for controlling the emission of sulfur oxides
from power generation. Their programs are designed to promote
intensive searches for new sulfur control processes having long-
range potential effectiveness at reasonable costs to a greater
extent than processes currently availabLe. Controls of sulfur
emission are desired for both power plants and other sources. One
phase of this overall program involves the development of new
processes aimed primarily at providing second generation processes
for removing oxides of sulfur from flue gases resulting from the"
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combustion of fossil fuels containing sulfur. The need for such
new processes is indicated by the economics, efficiency, and by-
product limitations of suth first generation processes now being
studied as limestone sorption and adsorption, and the alkalized
alumina processes. As a part of the nAPCA new process development
program, the FMC Corporation made a literature study to assess the
possible utilization of non-oxide inorganic solids for sulfur
dioxide removal processes. The results of this study conducted
under Public Health Contract No. 22-68-57, are reported herein.
- 3 -
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SCOPE OF WORK
Work conducted under this contract included a literature survey
on the use of inorganic solids other than metal oxides for S02
removal, a review of existing processes which fell within the
definition of the study, and thermodynamic calculations designed to
study the feasibility of reactions suggested for future study.
The literature survey included the following:
1.
Assembling data on the kinetics and equilibrium of sorption
of S02 and S03 on various sorbants.
2.
Surveying available data on the catalytic oxidation of S02
to S03 on inorganic solids other than dry metal oxides,
under conditions representative of industrial stack gases
and at temperatures where the sulfuric acid formed remained
on or within the catalyst as a condensed phase.
3.
Reviewing the chemistry and kinetics of reactions that
might possibly be used to regenerate spent sorbents. Such
reactions included thermal dissociation, oxidation, and
reduction.
4.
Surveying the chemistry and kinetics of
catalytic conversion of regenerated gas
useful sulfur-containing compounds, and
elemental sulfur.
the thermal and/or
streams to more
particularly to
5.
Surveying the literature for materials o~ construction
to be specified for use in the presence of gas streams
prevailing in stack gases or likely to be produced in the
regeneration of S02 sorbants.
6.
Studying analytical and laboratory methods used in S02
removal investigations and processes. Such studies were
made to obtain a- clear evaluation of the data and to obtain
possible information helpful in proceeding in subsequent
phases of this program.
All S02 removal processes described in the literature which fell
within the- definition of this study and which had been studied in
pilot plant, semi-commercial, or commercial installations, were
reviewed critically. This was done to acquire a better background
into the problem and difficulties that would be encountered in
developing such processes, and to obtain a full understanding of
the data needed to develop satisfactory processes.
Pertinent thermodynamic data located in the literature and
those received from Tracor, Inc., were collected and were embodied
in computer programs which were designed to calculate the thermo-
- 4 -
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I~
dynamic feasibility .of reactions of interest. . This program was
conducted to obtain a basis on which to establish the thermodynamic
feasibility of reactions which the literature survey indicated to be
worthy of future study.
The literature survey was conducted throughout the duration of
this contract. The other tasks were conducted during the last four
months of the contract. All studies were completed between July 1,
and February 24, 1969. .
1968
- 5 -
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CONCLUSIONS
Based on the literature review and on thermodynamic calculations
made from what are believed to be the most reliable available data,
the following five approaches are sufficiently promising to warrant
conducting la~oratory studies to prove their soundness and to
develop information needed for further process development:
1.
Carbon Regeneration
Present carbon-based processes are severely limited by the
requirements of the available regeneration schemes. Thermal
regeneration consumes carbon and hyperactivates the sorbent.
Regeneration by washing produces weak acid. Regeneration by
reduction of the sorbed acid to S02 with a gaseous reductant
would circumvent the degradation of sorbent while retaining the
other advantages of thermal regeneration. Thermodynamically, this
approach is possible~
II.
Evaluation of Doped Silica Gels
Silica gel, a highly porous matrix which is inert to sulfuric
acid, has a modest sorptive capacity for sulfur dioxide. By adding
to the gel minor components which are catalytic for the oxidation
of S02, it should be possible to prepare an adsorbent which may
adsorb S02 like carbon but which is a regenerable sorbent.
III.
Metal Disulfide Sorbents
Nickel disulfide is reported to chemisorb S02 at 150°C
release the S02 at somewhat higher temperatures. This will
verified, and other transition metal sulfides, particularly
will be tested for similar activity.
and to
be
FeS2
IV.
Ferric Hydroxide Sorbents
Ferric hydroxide should be investigated in an effort to find
forms which are highly active and which will not be deactivated under
adsorption process conditions. Its adsorptive capacity for S02 is
reported to be favorable.'
V.
Fly Ash as Lime Carrier
Methods of modifying fly ash to make it a suitable support
for hydrated lime in a process similar to the Still process should
be studied.
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RECOMMENDATIONS
It is recommended that laboratory studies be conducted to
obtain the data required for the necessary process engineering
analyses in areas where process concepts have been defined. In
addition, a laboratory screening program should be instituted to
evaluate S02 sorption-desorption characteristics of potential
new candidate materials for which there are only limited laboratory
data. The data from these laboratory studies should be utilized
to develop process flow sheets.
- 7 -
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i
ACKNOWLEDGEMENTS
This study was conducted by the FMC Corporation at the
Chemical Research and Development Center in Princeton, New Jersey.
Mr. R. Bloom, Jr. was Project Manager, Dr. C. A. Gray the Project
Scientist, and Dr. L. D. Friedman the Principal Investigator.
The literature search was conducted by Dr. H. Perkins. This
report was written by L. D. Friedman and C. A. Gray.
- 8 -
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SECTION I
INFORMATION SEARCH AND STORAGE
A.
PURPOSE
The purpose of the search was to obtain as much information
as possible on the removal of sulfur dioxide from gases by inorganic
solids other than metal oxides. Since the development of potential
systems depended almost entirely on the results obtained from the
literature survey, the survey was the first part of the program
that was started and it was continued throughout the duration of
the contract. The search concentrated principally on adsorption
reactions and mechanisms. This approach was followed on the theory
that no satisfactory S02 removal process could result unless a
feasible adsorption process were developed. While this approach
places the major emphasis on adsorption studies and mechanisms,
references containing material believed to be pertinent to potential
or appropriate desorption methods were also taken during the course
of this investigation.
B.
SOURCES SEARCHED
The major sources searched in conducting the literature survey
are listed in Table I. These include Chemical Abstracts from 1907
to date, the Engineering Index, and the Uniterm Index to chemical
patents. In addition, general review articles and bibliographies
of literature for the past ten years were reviewed to obtain an
overall picture of the general background and current status of
problems and available solutions. Specialized journals, such as
Air Pollution Control Association Abstracts and Fuel Abstracts and
Current Titles, etc., w~re also covered.
Over 1000 references were taken during the literature review.
In most cases, the evaluation of the article was made from the
abstract of the reference or the patent. However, references which
appeared to be of particular interest to this study were ordered,
and during the course of this survey about 75 actual papers were
obtained for more complete study and an additional 50 or so papers
were already available in the FMC library.
C.
SCOPE OF THE SEARCH
The literature was searched for references to all materials
which are within the scope of this contract and which adsorb or
react with S02' The materials falling within the scope of this
contract include clays, mineral products such as diatomite, industrial
wastes, inorganic salts,-metals and-alloys, covalent compounds,
non-metallic elements, oxides of non-metals, and hydroxides.
Both natural and modified clays were considered under the
clay subheading. The principal industrial wastes for which
references were found were fly ash and slag. Covalent compounds
- 9 -
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TABLE I
SOURCES CONSULTED IN THE LITERATURE SEARCH
ON S02 REMOVAL FROM FLUE GAS
Chemical Abstracts, 1-66(1907-June 1967)
Sulfur dioxide
Chemical Abstracts, Keyword Index, 67 (1)-68 (26) (July 1967-
-- -- Dec. 1968)
Absorption
Adsorption
Copper-nickel alloy
Desu1furization
Ferr i. . .
Ferro. . .
Fly ash
Iron carbide
Iron hydroxide
Iron sulfide
Nickel-copper alloy
Nickel sulfide
Silica gel
Sorption
Sulfur dioxide
Sulfur oxides
The Engineering Index (1931-1968)
Air pollution
(nq subheading)
Research
Flue gas
Sulfur
Recovery
Sulfur compounds
Sulfur dioxide
Sulfuric acid
Uniterm Index to (U.S.) Chemical Patents (1952-0ct. 1968)
Sulfur dioxide
Current Chemical Patents (selected for the FMC Corp.
Research Dept. from the Official U.S. Patent Gazette
Patent Abstracts for Belgium, France, Germany, Great
the Netherlands, and Japan.)
Vol. 1 nos. 1-4, 6-8, 11, 13 (1966);
Vol.. 2 nos. 1-9, 11-20 (1967);
Vol. 3 nos. 2-20 (1968).
Sulfur dioxide removal fro~ flue gas.
- 10 -
Central
and Derwent
Britain,
-------
TABLE I (cont.)
Air Pollution Control Associations Abstracts
Vol. 14 nos. 1,2(1968): vol. 13 nos. 1-12 (1967):
Vol. 12 nos. 1-9,11,12 (1966): vol. 11 nos. 3-5,7-12(1965).
General aspects
Control methods
Basic sciences - technologies
Fuel Abstracts and Current Titles 3(7) - 7 (12)
(July 1962-Dec. 1966).
Sulfur dioxide
[}
Research Association Month1
1968 .
Bulletin
u.S. CFSTI, SB-448, Rev. Supp1. 1:
~Air Pollution and Purification." (Lists reports and translations
dealing with air p611ution added to the CFSTI collection Sept. 1963
through March 1965).
Bituminous Coal Research, Inc. (J. W. Igoe) , "progress Report
on Research on Methods for Control of Sulfur Dioxide
Emissions from Coal Burning Power Boilers." Report L-273
(7 March 1968).
d
Anna Grossman Cooper, Sulfur Oxides
A Bibliography with Abstracts, u.S.
and Welfare, Public Health Service,
D.C. (1965).
and oth~~u1fur Compounds -
Dept. of Health, Education,
Div. of Air Pollution, Washington
International Chemical Engineering 2 - 8 (1961-1968).
Table of contents
Arthur M. Squires, "Air Pollution: The Control of S02 from Power
Stacks Part II - The Removal of S02 from Stack Gases." Chern. Eng.
Zi (24, 133-40 (20 Nov. 1967).
List of 34 references
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TABLE I (cont.)
"Proceedings Digest of the 6lst Annual Meeting Air Polution
Control Association, St. Paul, Minn." (23-27 June 1968).
U. S. Bureau of Mines Bull. 537, "Air Pollution", by S. G.
Davenport and G. G. Morgis (1954)1
Recovery of gases and fumes.
- 12 -
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included carbide, borides and nitrides. The only non-metallic
elements found were silicon and carbon, and virtually all
references under this category dealt with carbon. Carbon accounted
for more than one-third of all references covered. The only oxide
of a non-metal found in the literature was silica, the oxide of
silicon.
Oxides of metals fall outside the scope of this contract and
were not included in the bibliography. Compounds such as ferrites,
molybdates, vanadates, etc. which can be considered either as salts
of oxy acids or as mixed metal oxides were included in this survey.
The scope of the contract included these substances as adsorbants
for removing S02 but did not include them as reactants for removing
S02. This avoided duplicating work being done at Tracor, Inc.,
under a similar contract where the emphasis is on the chemical
reaction between metal oxides and S02.
Some references included in the bibliography do not discuss
suitable adsorbants or reactants but contain information believed
to be useful for devising recovery processes, performing economic
evaluations, designing reactors, etc. Other references included
were those containing standard thermodynamic values and a
representative number of general review articles on methods for
solving the S02 air pollution problem. References dealing with
the catalytic oxidation of S02 as used in the contact process for
making sulfuric acid usually were not included in this bibliography.
However, some of these references were taken and cataloged. A
separate file of references dealing with the analytical determination
of S02 was collected and given to the Analytical Department for
possible use in studies to be conducted during Phase II of this
contract.
D.
REFERENCE CODE SYSTEMS
1.
McBee Card Coding System
. All references were placed on McBee code cards KD-581B.
Where the reference was short or was taken from an abstract
publication, the entire reference or abstract was glued to the
McBee card. This eliminated the necessity of abstracting references
with the possibility of omitting critical data. Longer references
were abstracted on the McBee code card. For identification purposes
each reference was assigned a unique I.D. number that is indicated
on the corner of each McBee card. (See Figure 1)
The information on the McBee cards was coded to include:
(1) the nine compound categories that were indicated above; (2) the
type of reference; (3) the description of the information; and (4)
the element combinations which were discussed in the original
article. The code system used is shown in Table II. The reference
. type indicated whether a reference was a patent, paper, report, or
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Additional
Def'criptors
Rt::Iel'(~nCe
Type
II)
J.t
o
+-'
Q.
.....
J.t
,()
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'4)
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,- ~; adscorbcnts Iond catalysts. Ermolr,ul:o,' N. F.; Em101cuko, '-'I' '
',H ... ~ : E. N.; Popko,.jeh; G. A., VeslJi Akad. Navllk nt/ams. SSR, I ~ ,.
, " ': Ser. Khilll. Nal'lIk 1967, (3), 8-22 ,(Russ). A series of corptd. t=:1 ' ",
.. '" .;\ : and calcined oxide systems were studied hy thermogravimetry, I)','" '
f'$ ; D.T.A., and x-ray dilfraction., In the system Sio.-Mr;(OII).. I""
- 1) .: copptd. samples were compared with mcch. mixts, Due to the fO-: '
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...: ::! 31 T14D, SiOz
-, ::? 21 T6, Mg
'N ;! 17 ,T12, OB
45 - BU, Cr
.. ~ 19 T4, Fe
"
..., ~ 24, - TS, Ni
o :: 90 L5, sorbellt
.. 98 - preparation
.. ~
.:.
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Figure 1
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14
II)
s:J
o
..~
....
rJ
s:J
....
.0
E
o
u
...
s::
S
4>
.....
~
'tJ
~
CI1
'II)
+-'
s:J
4)
S
4)
....
~
II)
J.t
4)
~
s:J
~
-------
TABLE II
REFERENCE CODE SYSTEM FOR MCBEE CARD PUNCHING
Compound Type
clays, natural and modified
mineral products (asbestos,
diatomite)
industrial wastes (fly ash, slag)
inorganic salts
metals and alloys
covalent compounds (carbides,
borides; nitrides)
nonmetallic elements (silicon,
carbon)
oxides of nonmetals (silica)
hydroxides
Reference Type
patent
book
reports
meetings
RO
RI
R2.
R4
R5
R6
R7
R8
Tl2
LI
L3
L4
L4
Description of Information
general review
flue gas
plant operation
economic discussion
bibliography
sorption
oxidation of SO
chemical reacti6n
desorption
thermodynamics
kinetics
Elements and Element Combinations
aluminum
aluminosilicates
alkali metals (Li, Cs, Rb)
barium
bismuth
boron
cadmium
calcium
carbon
Reinluft carbon
carbonate *
chromium
dolomite
chlorine
cobalt
copper
gallium, indium, or thalium
hafnium
hydroxides
iodine
iron
lead
magnesium
manganese
TIO
TII
T5D
B24
B21
B25
B26
. T28
TI
TID
T9
B22
T9D
T26
T23
T21
TIOD
Tl9D
Tl2
T25
T4
T3
T6
T7
* C (8) is not punched for COj2 group.
- 15 -
molybdenum
nickel
nitrogen
phosphorus
platinum
other platinum metals
potassium.
silicon
silica
fibreglass
bag filterhouse
silver
sodium"
sulfur
sulfite or sulfate
tantalum
tin
titanium
vanadium
alkali metal-vanadium
compound
zinc
zirconium
B5
B9
B9D
BIO
L2
L5
L6
L8
L9
LIO
LII
T22
T8
T27
T24
Tl8
Tl8D
T2
Tl4
Tl4D
T13
T13D
T20
T5
Tl5
Tl5D
B23
B28
Tl7
Tl6
Tl6D
B27
Tl9
-------
meeting. Headings classifying ~he description of information
included general review, flue gas, plant operation, economic
discussion, bibliography, adsorption, oxidation of S02, chemical
reaction, desorption, thermodynamics and kinetics. Forty-three
elements and element combinations were coded on the McBee cards.
In addition, special entries were made for Reinluft carbon process,
fiberglass, bag filterhouse, and alkali metal-vanadium compounds
since these were all mentioned in so many abstracts.
The location of each of these headings on the McBee cards
is indicated in Table II. Each designation has a letter and a
number. The Rand L refer to the R&L numbers on the right and left
sides respectively, of the McBee keysort cards. "T" refers to the
numbers at the top of the McBee cards, and "B" to the numbers at
the bottom. The letter "0" after a number, such as T140 after
silica, indicates that this is a deep punch. Thus, the element
silicon is T14, but silica is T140. Silicon references will be
included in silica references and would be recovered by the use
of the searching needle to separate out those McBee cards contain-
ing a punched card for T14. However, the reverse would not be
true.
Some rather arbitrary decisions are incorporated in the
classification system used. Each potential adsorbant or reactant
is classed under the first appropriate heading shown in Table II.
Thus, silica is classed under oxides of non-metals but not under
covalent compounds. Similarly, clays are not additionally classed
under mineral products. A reference can have two material class-
ification numbers if it describes two materials which belong to
different material classes, such as references discussing both
silica and carbon. A,salt such as calcium sulfide is described
by the T28 code for calcium plus the TIS code for sulfur. Thus,
salts are listed under both anion and cation. Element groups,
such as SO~ and Si02 are used instead of the simp+e element codes
for Sand Si. However, references coded on the McBee cards
contain both element and element group code numbers by using the
McBee deep punch. Thus, for example, So~ is the TIS deep punch
for sulfur. Sulfur itself is TIS.
Several descriptors may be used to describe the types of
information in a reference in addition to those for specific
types or compositions. For example, an article which discusses
adsorption and desorption of S02 on silica is coded under both LS
and L9 which are the codes for adsorption and desorption. If the
article also refers to S02 in flue gas, then the B9 code for flue
gas will also be used. This coding arrangement permits a rather
general classification of the various references and at the same
time eliminates many references that are not specific for individual
headings.
- 16 -
-------
2.
Computer Coding System
When it became evident that the number of references was
becoming too voluminous to be handled easily by the usual McBee
card handling techniques, it was decided to computerize the
bibliography. This had the advantage of allowing rapid printouts
of selected references, giving rapid and accurate alphabetization,
aiding in making specialized searches, and allowing expansion of
the coding system that had been used. Consequently, the information
on the McBee cards was prepared for a computer system and this
information was stored on cards.
Because of the vast amount of time that had been spent
coding the references in the McBee cards, it was decided to use
a computer coding system which would be based on the classification
used on the. McBee Keysortcard~ This procedure had the advantage
of using the existing classifications tha~ were immediately
available, and while this was not the optimum method to use in
computerizing the information, it gave a computerized reference
system in the shortest time and with the least expense.
The computer code system finally adopted uses a two
digit number to describe each reference type and up to 15 three
digit numbers per reference to classify the adsorbent or reactant
and to indicate the main points of emphasis in the reference. The
use of 15 three digit numbers to qualify a reference was arbitrary.
This number could be expanded to any number desired, but it was
felt that for our purposes 15 classifiers could adequately describe
virtually all the references.
Reference. Type
The reference type, indicated by a two-digit number,
classifies the reference as a journal article, paper presented
at a meeting, report, book, article in an irregular publication,
a patent, or other type' such as private communication. Table III
lists the reference types with their corresponding computer and
McBee code numbers. Patents are coded for the computer with
numbers greater than 10, non-patents with computer-code numbers
less than 10. One example of the greater flexibility obtainable
with the computerized code was the ability to break the Ll McBee
Patent code into eighteen codes to indicate the country of origin
of each patent. .
a.
Reports under the 01 computer code include publications
by Government agencies such as the u.S. Bureau of Mines, or companies,
such as Dow Chemical Company. References to papers presented at
meetings are classified as such even when the proceedings are
issued later in journals or in book form.
- 17 -
-------
TABLE III
REFERENCE TYPE CODES
Code Code
Computer McBee Computer McBee
journal 00 (none) Danish 16 (Ll)
report 01 (L4) French 17 (Ll)
meeting 02 (L4) German 18 (Ll)
book 03 (L3) German (E) 19 (Ll)
irregular publication 04 (none) Hungarian 21 (Ll)
others 05 (none) Italian 22 (Ll)
Patents
U.S. 11 (Ll) Japanese 23 (Ll)
Australian 12 (Ll) Netherlands 24 (Ll)
Belgium 13 (Ll). Russian 25 (Ll)
British 20 (Ll) Swedish 26 (Ll)
Canadian 14 (Ll) Swiss 27 (Ll)
Czech 15 (Ll) Yugoslavian 28 (Ll)
- 18 -
-------
b.
Material "Class
All potential adsorbents and reactants are divided into
the nine material classes which were established as the basis of
reporting needs of the present contract and given the code numbers
shown in Table IV. References which do not discuss a potential
adsorbent or reactant have no material class classification. Thus,
standard thermodynamic references do not receive such a classification.
Each potential adsorbent or reactant is classed under
the first appropriate heading in Table IV. Thus, following the
system described above for the McBee card classification, silica is
classed under nonmetals but not under covalent compounds, and
clays are not included under mineral products.
c.
Elements and Element Combinations
The code descriptors listed in Table V were used to
assign computer code numbers to elements and elemental compositions.
For example, CaS is described by both an 007 (T28) code for Ca and
an 036 (T1S) code for S. In addition to simple elements, Table V
also contains some codes for element groups, such as S04 and Si02
which are used (if appropriate) instead of the simple element codes
for Sand Si. Thus, to perform a complete computer search for all
references to sulfur "compounds one must check references whose
code cards contain both 036 (sulfur) and 037 (sulfate). All
elements listed under more than one code are listed in Table VI.
The "large number of metals" category is used when the
enumeration of all metals listed in a reference would produce
more than the 15 allowed three-digit computer code numbers. In
these few cases, those elements judged most pertinent were coded
individually and the others were indicated by the "large number
of metals" code.
d.
Additional Descriptors
The descriptors in Table VII indicate the nature of the
information contained in a reference. For example, an article
. which discusses the sorption and desorption of S02 on carbon is
" described by 090 (LS) for sorption and 093 (L9) for desorption.
If the S02 is in flue gas, then 081 (BO) for flue gas is also
used. If the oxidation of S02 and its chemical reaction are thought
to occur with one substrate both the 091 and the 092 descriptors
may be used.
Four terms having no McBee codes were added in the
final phase of the search when their inclusion seemed advisable.
The processes and systems code includes references to systems
definitely outside the scope of the contract, such as the Bureau
of Mines' alkalized alumina process. "
- 19 -
-------
TABLE IV
COMPUTER CODE FOR GENERIC MATERIAL CLASSES
FOR S02 REMOVAL FROM FLUE' GAS
clays, natural and modified
industrial wastes (fly ash, slag)
mineral products
(asbestos, diatomite, natural zeolites)
oxides of nonmetals (silica)
hydroxides (Mg(OH)2' FeIII hydroxide)
nonmetallic elements (carbon)
metals and alloys (platinum)
inorganic salts
(ferrites, sulfides, synthetic zeolites)
covalent compounds (carbides)
20 -
Computer
Code
070
- 072
071
078
017
077
075
073
076
McBee
Code
(RO)
(R2)
(Rl)
(R8)
(T12 )
(R7)
(R5)
(R4)
(R6)
-------
TABLE V
COMPUTER CODE FOR ELEMENTS AND ELEMENT COMBINATIONS
Code
Computer""""McBee
aluminum
aluminosilicates
... i, Cs, or Rb
barium
bismuth
boron
cadmium
calcium
carbon
carbonate
chromium
dolomite
chlorine
cobalt
copper
gallium, indium,
or thalium
iodine
iron
lead
magnesium
manganese
molybdenum
nickel
OOl-TlO
002-Tll
003-B18
004-B24
046-B2l
OOS-B2S
006-B26
007-T28
008-Tl
OlO-T9
04S-B22
Oll-T9D
012-T26
013-T23
014-T2l
OlS-B19
018-T2S
019-T4
020-T3
02l-T6
022-T7
023-T22
024-T8
- 21 -
nitrogen
phosphorus
platinum
Ru, Rh, Pd,
potassium
silicon
Os, or Ir
silica
fibreglass
silver
sodium
strontium
sulfur
sulfite or sulfate
tantalum
thiocyanate
tin
titanium
tungsten
vanadium
alkali metal-vanadium
compound
zinc
zirconium
large no. of metals
Code
Computer McBee
02S-T27
026-T24
027-T18
028-B20
029-T2
030-T14
03l-Tl4D
032-T13
034-T20
03S-TS
047-none
036-TIS
037-TISD
038-B23
OSO-none
039-B28
040-T17
048-none
04l-T16
042-T16D
043-B27
044-T19
OSO-none
-------
TABLE VI
ELEMENTS INCLUDED UNDER MORE THAN
ONE COMPUTER CODE LISTING
Element Code Numbers
aluminum 001 or 002
Li, Cs, or Rb 003 or 042
calcium 007 or 011
carbon 008 or 010 or 011 or 050
magnesium 021 or 011
nitrogen 025 or 050
potassium 029 or 042
silicon 030 or 031 or 032 or 002
sodium 035 or 042
sulfur . 036 or 037
vanadium 041 or 042
- 22 -
-------
TABLE VII
ADDITIONAL COMPUTER DESCRIPTORS
general review 080 (B5D) sorbent preparation 098 (none)
flue gas* 081 (B9) sorption 090 (L5)
plant ope~ation+ 082 (B9D) oxidation of S02 091 (L6)
engineering 099 (none) chemical reaction 092 (L8)
processes and systems 097 (none) desorption 093 (L9)
Reinluft process 009 (TlD) thermodynamic data 094 (LlO)
bag filterhouse 033 (T13D) kinetics 095 (Lll)
economic evaluation 083 (BlO) recovery 096 (none)
literature survey 085 (L2)
* Compositions like that from power plant stacks and
not smelter gases or tail gases from manufacturing
sulfuric acid.
+ Includes description of pilot plant operations.
- 23 -
-------
Because it is mentioned so often, the Reinluft process has a
separate code. Recovery can refer to either recovering the
sulfur value in the flue gas or generating the spent adsorbent
or reactant. Engineering is used to indicate information such as
gas-solid contacter designs.
3.
Computer Input
The computer input for each reference consists of from one
to eight cards (usually 2 or 3) which contain the citation plus one
card which contains all numeric code information. The cards
containing the citation are numbered sequentially (starting with 1)
in column 80. The code card (also called the 9-card because it
contains a 9 in column 80) is the last card for a given reference
and contains all the code numbers. All cards belonging to one
reference contain its identifying (I.D.) number in columns 76-79
for non-patents or in columns 75-79 for patents. A variable
number of blank columns occur prior to the ID number since it is
undesirable to have words split arbitrarily. The coding system
is discussed more fully below.
Citation Input
The format used for keypunching the citation has been
standardized to allow computer searching for authors, titl~,
journal, patent number, and year. These five items have specific
tags by which the computer can identify them.
a.
(1)
Author Information
Author information is always at the beginning of the
citation and includes individuals, companies or government agencies
issuing reports, assignors of patents, and inventors. Several
examples follow:
1
2
3
4
5
*Smith I M, Taylor R P, Jones H K, et al.*
*Dow Chern Co* (Smith I M, Taylor R P, Jones H K, et al).
*Dow Chern Co*
*U S Bur Mines* (Smith I M).
*Smith I M, Taylor R P*
The author information for a journal article (or an unassigned patent)
is keypunched as in example 1 for more than three authors (inventors)
or as in example 5 for two authors (inventors). The author information
for an assigned patent with inventors Smith, Taylor, Jones, et al.
is keypunched as in example 2, or, if the inventors are not known,
as in example 3. Reports are keypunched as in example 4 (Smith
is the author) or example 2 (Smith, Taylor, Jones, et al. are the
authors and Dow Chemical Co. is issuing it). The first asterisk
occurs in column 1 of card 1 and the first period always occurs
at the end of the author information. This period is sometimes
followed by an asterisk.
- 24 -
-------
(2)
Title'
The title is always the second unit of a citation.
It is immediately preceeded and ended by an 028 multipunch. The
028 multipunch indicating the beginning of the title sometimes
occurs directly after the period-asterisk ending the author
information, sometimes directly after the period ending the
author information, sometimes one blank column removed from the
period ending the author information, or in rare cases (when
the author information uses the whole first card) in column 1
of a new card. The KWIC mark prints out as a dash (see Keypunched
sample in Table VIII).
(3)
Journal
The journal name is the third piece of information
for journal references. Its name is immediately preceeded and
followed by the slash symbol, the I. This slash1 occurs immediately
after the second 028 KWIC mark, or in column 1 of a new card
when appropriate. periods are used after abbreviations in the
journal names. Because Chemical Abstracts has changed its
abbreviations several times over the past fifty years and also
because references were obtained from other sources which use
different abbreviations, a computer search was performed for journal
names and an alphabetical listing produced. This ensured that
all references to a given journal had an identical abbreviation.
Slashes are also used to indicate location of other non-patent
references, such as meetings, conferences, etc.
(4)
Year
The year usually is placed in parenthesis at the
end of a reference. However, if a journal has no volume number
the year will be placed immediately after the name of the journal.
When the year is at the end of a journal reference, it may be
accompanied by either the day and month or by the month alone.
Thus, referring to Table VIII, reference number 0065 is dated
August, 1967, whereas reference 1008 is dated 20 Dec. 1967. Patent
dates always contain the day, month, and year. The < symbol is always
placed before and after the year so that there can be no confusion
as to which number constitutes the year of the reference. Commas,
parenthesis, and periods may also be included. Examples include
(27 June < 1968). <,<1968<, (1968). The < symbol prints on the
reference sheet as a square (see Table VIII) .
IThe slash is also used to indicate patent numbers.
- 25 -
-------
FERRUARY 24, 1969
TABLE VI II
SAMP~E REFERENCE SHEET AS KEYPUNCHED
PAGE
._-_._,--~--~- .. --. .. .- --- .-. ..- ..
. ..- '."---.--"
1
2
3
4
~
b
7 .
II
9
10
11
I -'---1:2-----
13
14
15
16
17
----1'8--
19
20
71
22
23
- ---2'4----
25
26
27
711
I'..)
0\
*ORATWA H, JUENTGEN K, PETERS W.*-MECHANI,SM OF FORMATION OF SULFUR OIlJXIDE 00651
ON ADSORPTION COKE USED IN DRY WASTE GAS PURIFICATION.-/CHEM. INGR. TECH./ 00652
39 (16), 949-55 IAUGDI967).D 00653
00008090091093077 ' 00659
*GAUBE J, KNACKE 0, LYOTIN H, ET AL.*-METALLURIGICAL PHASE DIAGRAMS OF 00931
1 KUN L.UMPULJNIJ~. -7lfR1:l;; 1:.1 Stf'lHUt.1 I'FN\~r;-T3?t'r9T;'()5"~-=BiJn-903T-.-iJ- _P.- -------- --. .-_.'--01'')'1"3"2- - ... .-- - --
00019036037094092073 00939
*DRATWA H, JUENTGEN H.*-DESULFURIZATION OF SMOKE GASES WITH ARSOkRENT 03551
CHARCOALS WITH DIFFERENT PROPEIHIES.-/STAlJH, REINHALTUNG LUFT/27 (7), 301-703552
DI1967).D - - 03553
00008081090095093077 03559
*LJ :-, NA I L At:KUI'IAlJT1C"S-I\NIJSVtlCFII:[JHTN":~frjlllC13RTDE--B---S;-FrETMEL-S-,--EH[ER"S"T-G;----O-5TBT-'--'-- .
ET AL).-THERMODYNAMIC PROPERTIES TO hOOO UEG K FOR 210 SU8STANCES 05182
INVOLVfNGTHE-F1RST 18 ELEMENTS.-SP-3001, WASHINGTON, 0.C.D(1963).D 05183
01094 051R9
*U S BUR MINES*IKElLEY K K).~CONTRIRUTIONS TO THE DATA ON 'THEORETICAL 05151
METALLURGY. VII. THE THERMODYNAMIC PROPERTIES OF SULFUR AND ITS 05152
I NUKGAN rC----ClJM'Pl1UNDS-;-=?BULT;-TZtITb-1J1T~3'6-) ;ElREPKINTEU-f'I"f't3UC'["; -601 IT9"6'OT~ -- -----'-()5T5'3" - . - - .-- ---,'" ---- -. .
01094 05154
*TRACOR CORPORATION.*-THERMOOYNAMIC PROPERTIES OF SELECTED METAL 0511]
COMPOUNDS.-/PRIVATE COMMUNICATION/Ill NOVD1968).D 05117
05094 . 05119
*OON CHEMICAL COOl STUll 0 R).-JANAF INTERIM THERMOCHEMICAL TABlES.- 0526]
"MTDT1XN!Jt--MTCR--.r:tn"700TDEr-s-rn--.--'-------------- ---..------- -- - ----.- - .------. 052(-,'7.--
01094 05269
*BIlLINGE B H-M.*~THE CHEMISORPTION OF SULFUR DIOXIDE ON CARBONS.-/CONF. 04291
IND. CARBON GRAPHITE, PAPERS, 2ND, LONDON/19b?, 398-404 (PlIB.n1966).n 04292
02090008077093 04299
.---.----.
----._------- _. --. -~-- . --.- ----_.~.._-~---------- .--.--. -_._---- _._-~_. -. -_...
- - _.-~ - ..
-------
(5)
Patent Number
In classifying patents, the third piece of keypunch
information is the name of the country of origin, abbreviated with
no period, followed by a slash (/), the patent number, another
slash (/) and then the date. For example, Brit/l,054,798/
(27 Nov <1965).< Note that a search for a patent number requires
searching first for the reference type code corresponding to the
desired country followed by a search for the patent number.
b.
Code Input
The code card accompanying each citation contains the
two-digit code number for reference type in columns 1 and 2, and
up to the maximum of fifteen three-digit code numbers in columns
3-48. The three-digit code numbers can be arranged in any order.
4.
Function of Computer Programs
Listing Program - 1
This program lists the file of cards punched according to the
coding system described in IV above in the general format used in
this report (format l)~ Specifically, this program
(1)
(2)
(3)
(4 )
(5)
(6 )
deletes *,/,<, and the 028 multipunch from the print out
deletes the I.D. code number from all cards except the
code card
deletes the digit punched in column 80. This is the
card number for each reference when more than one card
per reference is used.
corrects the left hand margin of the 1st card of a
reference for the deleted*
inserts one space between each code number listed on
the 9-card
inserts a blank line between the 9-card of one reference
and the beginning of the next reference.
Listing.Program - 2
This program lists the references in format-l except that it
numbers the references in sequential order. This order may be
alphabetical by author, by codes, or by the I.D. number.
- 27 -
-------
,------
~
Code-Search Program - 1
This program can print out in format-l references whose
9-card contains a given three-digit code number. Since the
appropriate references are listed in the same order as they
occur in the file, the alphabetical file is used for making
alphabetical listings.
Code-Search Program - 2
This program lists the reference I.D. numbers of all references
which do not contain a three-digit code number of the form 07X where
X can be 0, 1, 2, 3, 4, 5, 6, 7, or 8. This program was used
to check that all appropriate references had a material class
code number.
I.D. Search Program - 1
This program lists in format-l references corresponding to
the indicated I.D. numbers. An alphabetical listing is produced
when applied to the alphabetically arranged deck of cards.
Bibliographic-Information Search Program - 1
This program produces a deck of punched cards (one per
reference) which duplicates the information (journal name) between
the two slashes (/) provided it occupies no more than 76 columns.
The last four columns of the punched card contain the reference
number. This is useful for collating all references from a given
journal (or source). If this deck of punched cards is alphabetized
by an 082 sorter and printed using a standard 80/80 listing, an
alphabetical listing of the journal names is obtained.
- 28 -
-------
SECTION II
- EVALUATION AND DISCUSSION OF THE RESULTS OF THE
LITERATURE SURVEY
During the course of this study, over 1000 references and
patents were evaluated critically. About half were rejected because
they were not considered pertinent to the project. Most of the
rejected references dealt with the use of platinum and vanadium oxides
materials to oxidize S02 to S03 for the manufacture of sulfuric
acid.
Our principal interest in this study was in determining the
state of the art for removing S02 from flue gases containing
only about 0.35 mole percent S02. Unfortunately, most references
that discussed the adsorptive behavior of or the reaction of S02
described the behavior of streams of essentially pure S02. Thus,
many of the reactions which involve S02 would not remove low
concentrations of S02 from flue gases. Whenever thermodynamic
data were available, the results were extrapolated from the S02
concentration reported to the concentration in flue gas.
All references were coded and grouped according to the generic
material classes, and each class was studied separately. In some
cases, the generic classes were broken down further. Thus, because
of the large number of iron references collected, the iron salts
were reviewed by themselves as a sub-group of the inorganic salts
class. The iron references included a few references from classes
other than the inorganic solids, such as iron-doped silica gel,
iron slags, etc.
From the review of the literature, those references which
appeared to be most interesting based on the degree of reactivity
reported with S02, or the quality and quantity of work done, or
the thermodynamic or other data listed, were collected. In a
few cases where available thermodynamic data were located, an
attempt was made to evaluate the thermodynamic potentialities of
the reactions described. The following nine sections describe what
are believed to be the most pertinent references located for each
of the nine classes into which our general cate00ry was hr"oken.
A.
Clays
The only clay mentioned as being an adsorbent for S02
is bentonite (245,429). A fairly recent reference claims that oxides
of sulfur are adsorbed strongly on acid-washed bentonite.
The heat of adsorption of water on activated bentonite is
two to three times that of the oxides of sulfur. (429) Because the
moisture content of flue gases is many times that of S02, it is
assumed that clays probably would adsorb moisture rather than the
S02. However, because of bentonite's relatively low cost and
- 29 -
-------
superior resistance to oxides of sulfur, bentonite may be evaluated
briefly with synthetic flue gas as part of our overall screening
technique development program in Phase II to verify our assumption.
B.
Mineral Products
Many investigators and organizations currently are
studying the use of lime and dolomite to remove sulfur dioxide and
other oxides of sulfur from flue gases. The processes under study
.are direct injection of lime into furnaces and flue gases followed
by scrubbing the waste gases with aqueous suspensions of lime.
Lime treatment has been discussed in great detail in many review
and specialized articles. Because of the wide-spread interest in
the use of lime for removing oxides of sulfur, it is felt that no
further studies with lime should be undertaken within the scope
of this contract.
u.s. patent, 3,286,106 describes the reaction of oxides
of sulfur on dry chrysotile asbestos Mg3Si20s(OH)~. It is claimed
that asbestos can combine with from 0.01 to 3.0 weight percent
sulfur and that the sulfurized asbestos is a superior filler for
vinyl tile. Asbestos would have excellent inertness to S02 but
its low adsorptive capacity would rule out consideration of its use
as an adsorbent for oxides of sulfur.
The possibility of forming fertilizer by reacting
phosphate rock with S02 gas has been studied (373,161). These
studies showed that a slurry of phosphate rock adsorbed enough S02
to make the phosphate soluble. This process was considered as a
possible means for making low cost fertilizers, but was abandoned
when it was found ,to,,"have no economic advantage over the use of
cqncentrated sulfuric acid. Dry treatment of a phosphate rock with
sulfur dioxide at temperatures above 95°C rendered about two-thirds
of the P20S available as a fertilizer. Part of the S02 was decomposed
to sulfur and some formed calcium sulfate and calcium pyrosulfate.
., . ..''':" '.:.0.:.; ~ '.
The investigators who studied the reaction of S02 with
phosphate rock hoped to use concentrated S02 gas rather than
sulfuric acid to manufacture fertilizer. Even though this reaction
did not appear promising, it is possible that phosphate rock could
adsorb substantial quantities of S02 from flue gases and that the
spent sulfated phosphate rock might then be used as feed to a
fertilizer plant. Since phosphate rock occurs in many parts of
this country and since the reaction with S02 occurs at temperatures
above the dew point of the two gases, it might be desirable to
examine the reaction of S02 with phosphate rock to determine
whether enough SOi could be adsorbed from flue gases to justify
the handling costs and to reduce the amount of sulfuric acid
required for fertilizer manufacture.
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C.
Industrial Waste
Several industrial wastes have been examined to determine
their ability for removing oxides of sulfur from flue gases. Two
recent patents claim the use of fly ash for the removal of S02 but
give little data on the type of fly ash used or the sorption
conditions studied (517, 473). Iwamura (166) claims that copper
blast furnace slag has good S02 sorption properties. A study of
the translation of this paper casts considerable doubt as to the
usefulness of such slag for removing S02 from flue gas.
Billings (39) discusses the removal of oxides of sulfur
by the use of mineral wool filters. Filters two inches thick and
with a density of four pounds per cubic foot removed 80% of acid
mist and 99% of acid gas and fumes. By washing away the iron
oxide and fly ash which became trapped in the filters, he was able
to reuse the filters 8 to 10 times with no apparent loss of S02
removal capacity. The removal of acid gas was improved by the
presence of moisture on the slag wool filters. Mineral wool filters,
according to Billings, have the advantage of low cost, small fiber
diameter, the ability to withstand temperatures of 1000°F, and the
ability to remove submicron particles from industrial furnace effluents.
Pressure drops across the filters were not stated. Because these
filters remove acid gases and mist so effectively, Billings suggested
a two stage process in which flue gas is oxidized at high temperatures
to convert the oxides of sulfur to S03 (using potassium oxide and
vanadia catalysts to effect the oxidation), and the acid mist is
removed on the mineral wool filter at temperatures just above 125°C.
He claims that this temperature is low enough to achieve good S02
absorption but high enough to make reheating of the gas unnecessary.
Red mud, a by-product of aluminum manufacturing which has
a relatively high iron oxide content, removed 70 to 75% of the S02
in a flue gas, according to a communication from the Republic Coal
and Coke Company. The process is being investigated in pilot plants,
but no commercialization has yet been attempted. Red mud has only
limited availability. Its properties vary from location to location
and generalization of its reactivity with S02 is difficult.
The Still process uses hydrated basic lignite ash to adsorb
S02 (350. This process is described in considerable detail on
pages 126-28. The lignite ash mayor may not be augmented or supplanted
with hydrated lime. The process operates in the temperature range
between 200 to 850°F. Oxygen and carbon dioxide do not interfere
with the operation of the process, according to the description of
the process in the literature. The reaction occurs in a transport
bed and is primarily the reaction of calcium hydroxide with S02.
Thermochemical data indicate that the reaction is highly favorable
and that the temperature of operation is limited only by the
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~
decomposition of the calcium hydroxide, which is above 580°C.
Regeneration is somewhat difficult because part of the calcium
sulfite that forms is oxidized to calcium sulfate which can not
be regenerated. Calcium sulfite can be decomposed thermally to
calcium oxide, which can be reused, and to S02, which can be
recovered. The adsorbent is inexpensive enough so that partial
regeneration may be practiced or the spent adsorbant may be discarded
entirely. A somewhat similar process was described by Herzog (153),
who combined S02 with the basic constituent of ash. His S02 removal
reaction is also based on the reaction of. calcium oxide with S02,
and according to the author is a promising commercial development
in East Germany.
The use of a fly ash to remove sulfur dioxide has
considerable merit. Many fly ashes are basic and their natural
basicity could be used to remove sulfur dioxide. In addition, it
should be possible to modify fly ash to make it a suitable support
for hydrated lime which would react with the oxides of sulfur. Such
a preparation would not be too different from that used in the
Still process, but it would be more generally available than the
lignite ash which the latter process uses. The difficulties
encountered in regenerating the adsorbant from the Still process
would not be a factor in the use of alkalized fly ash since the
wasting of a considerable amount of the spent fly ash would be
of slight economic importance.
Inorganic Salts
Over 200 references have been located which mention the
use of inorganic salts as adsorbers for S02. In many cases, too
little information was presented to permit a full understandina of
the processes involved and the papers were ordered. Several of
the reactions occur in high partial pressures of S02, but would not
be applicable for flue gas cleanup, based on simple thermodynamic
calculations. In other cases, such data were not available and
the reaction could not be evaluated properly.
D.
It would be expected that those elements which are
mentioned most often in the literature as being adsorbents for or
reactants with sulfur dioxide, would be the ones that would be the
most active and would be the element around which potential processes
should be considered. On this basis, the elements mentioned most
often in the literature are the alkaline metals of Group 1, the
alkaline earth metals of Group 2, and the transition metals of
Group 8 of the Periodic Table. Other elements mentioned less often
include aluminum, indium, tin, lead, vanadium, chromium, manganese,
and tungsten. The salts of these metals that are mentioned most.
often include sulfides, sulfites, sulfates, halides, c~rbonate~,
and ferrites. ~~o of the better known sulfur dioxides removal
processes use combinations of these elements. These are the Grillo
pr'ocess :md the sodium aluminate process.
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Nickel disulfide has some interesting properties for
reacting with S02. Nickel disulfide chemisorbs S02 at temperatures
of about 120°C, according to Budelot and Delafosse (54). The
article was concerned primarily with a sorption phenomena at these
temperatures and does little more than point out that chemisorption
exists, and appears to increase with increasing temperature.
" "Interestingly, nickel disulfide also catalyzes the reduction of
S02 at higher temperatures so that a potential process, based on
a chemisorption at 120°C, and desorption at temperatures above
200°C, would appear to be possible.
One problem in working with nickel disulfide is the fact
that the literature mentioned many nickel sulfide compounds. A
recent Russian article discussing the steady-state potentials of
nickel sulfides points out that samples containing from 21.1 to
35.44% sulfur showed markedly different chemical, microstructural
and surface properties.
-. - - .
An interesting thermodynamic analysis of the reduction
of sulfur dioxide bv metal sulfides with the formation of elemental
sulfur was prepared". by some Russian investigators (213). In the
case of sulfides of alkali and alkaline earth metals, these
investigators claim the equilibrium yield of sulfur at 500 to 800°C
was determined to reach 95+ weight percent with on" other by~product
gases being formed. By reactin~ with sulfur dioxide and oxygen in
the flue gas, the sulfides were converted to sulfates which can be
reconverted to sulfides by the action of a reducing gas. According
to these investi~ators, the equilibrium yields of the reduction
of sulfates to sulfides by carbon monoxide in the temperature range
of from 800 to 1100°C is over 90%.
Wohler, et al., describe the reaction of S02 with calcium,
iron, and zinc sulfides and with many ores, including pyrites (434).
At first glance, it would appear that iron sulfides should react
similarily to nickel sulfide and that this reaction was not unusual.
However, a thermodynamic investigation showed that the reaction of"
iron sulfide with S02 occurs only at relatively low temperatures
and probably at higher S02 partial pressures than would be obtained
from flue gas. British patent 726,216 claims the formation of
Fe30q and sulfur when a stream of oxygen and S02 are passed over
ferrous sulfide at 900 to 1000QC.
Sodium silicates have been reported to adsorb as
40 weight percent of S02 at temperatures of 300 to 550°C.
reaction is discussed in greater detail in the section on
below.
mud:
This
silica
Several investigators mention the use of barium salts
for the adsorption of S02 over the temperature range of from
100 to 400°C (165, 565, 548, 67). One reference claims that the
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sorptive action of barium carbonate was improved when the barium
carbonate was mixed with 20 to 43% of carbon (67). The function
of this carbon is not clear, since the abstract gives no indication
of the formation of carbonates or carbides.
rrdosanalyzed the properties of systems consisting of
gaseous ~n2, CO2, and a solid ffl8tal oxide with respect to the
equilibrium pressures of 802 (106, 107, 108, 109). In discussing
24 systems for removing 802 from flue gases, Erdoes considers
the C02 content of the flue gas to be sufficient to convert many
of the metal oxides. to metal carbonates at temperatures below
250°C. Thus, although he starts with metal oxides, he is really
discussing the adsorption of 802 on carbonates in many cases.
The reaction rate of sodium carbonate with 802 below 150°C is
quite dependent on the water vapor content of the 502-air mixture.
This was confirmed by Russi'an workers (195).
The reaction of 802 with phosphate rock was reported above.
It is interesting to note that the literature contain almost no
references to the use of phosphates for 502 removal~ The reason
for this apparent anomaly is not clear.
The survey of the adsorption of 502 by inorganic salts
suggests that some sulfides, particularly nickel sulfides, are worth
studying seriously as potential adsorbents for sulfur dioxide. Other
transition metal disulfides, particularly Fe52 should also be tested
for similar activities. We plan to evaluate the sorptive capacities
or abilities of many compounds using relativ~ly short reaction periods
under Phase II and will check out many of the other compounds that
have been mentioned repeatedly in the literature to oQserve their
reactivity with or sorption of 502 in concentrations approaching
those found in flue gases.
E.
Metals and Alloys
A large number of investigators have studied the adsorption
of 802 on metals and various alloys. Platinum on silica is mentioned
many times in connection with the conversion of 802 to 503 in the
manufacture of sulfuric acid. pevnyi (280) claims that at 450°C,
chromium-tin alloys activated by antimony have better adsorption
characteristics than either platinum or. asbestos or platinum on
silica gel. Barium-vanadium 'and barium-aluminum-vanadium alloys were
less active. The difference in sorption activities between all
these different alloys and metals disappear at 500°C. Danilova (70)
reports moderate reaction of 502 with zinc, cadimum, copper, and
lead~
pannetier has done extensive work on the reactions of
802 with nickel, iron, and cobalt (265, 266, 267, 268). He claims
that the reaction of 802 with finely divided nickel is very exothermic
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and proceeds rapidly at 460°C according to the equation: 7Ni+2S02=
4NiO+Ni3S2. Thermogravimetric and x-ray studies showed that
S02 reacts with Ni3S2 at 460-550oC to form NiO and NiS, and the
latter is fin~lly,transformed into NiO with more S02. The
advance 6f'~he interface is the limiting factor and the energy
of activation is 84 kcal/mole.
Rumyantsev (307) agrees that nickel reacts with S02
according to the equation shown above. He reports that a vigorous
chemical reaction starts at between 460 and 470°C but that the"
reaction is most nearly complete at between 600 and 800°C. He also
claims that reverse reaction is possible at temperatures above
800°C.
'Perhaps part of the difficulty is interpreting the data
from the reaction of nickel and S02 arises from the fact that
one of the products, nickel sulfide, also reacts with S02 to form
the oxide and sulfur. (See Section 4). However, the latter
reaction occurs at lower temperatures than those used by
Pannetier and Rumyantsev. In the temperature ranges they used,
the reverse reaction of nickel oxide with sulfur is favored.
Other. metals reported to react with 802 include
indium (263), rhodium (423), copper (314), magnesium (321), and
alkali metal sulfate-vanadium oxide mixtures (372). The reaction
between cobalt, nickel, iron, and indium with S02 is probably a
chemisorption reaction since the metal is usually converted to
the sulfide and oxide. . \"7ith nickel and cODal t, the reaction is
reversible at temperatures above 800°C. Indium requires higher
temperatures to give a reversible reaction.
Platinum is known to be an excellent adsorbent for
S02 but is not being considered because of its cost. However, a
nickel-copper alloy which is reputed to have the same electron
configuration as platinum is known. If this material can be
prepared its S02 adsorption behavior will be checked.
F.
Covalent Compounds
Our classification for covalent compounds includ~s
carbides, nitrides, and silicides. No nitrides, or silicides
were cited as being adsorbents for S02. It has been reported that
silicon carpides, or carborundum as it is better known, adsorbed
a negligible amount of S02. Nickel carbide adsorbs traces of S02
at ambient temperatures.
In the temperature range of 250 to 400°C, nickel carbide
reacts with S02 to form mainly C02 and NiO. Small amounts of Ni, Co,
Ni3S2 and sulfur also form.
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G.
Non-Metallic Elements
The only non-metallic element which adsorbs appreciable
amounts of 502 is carbon. At least three of the processes described
below as having been studied in commercial or semi-commercial plants
are based on the use of carbon as an adsorbent. As a result of this
interest in the commercialization of the use of carbon for 502
removal, a vast amount of work has been done studying the reactions
of 502 on or with carbon. Thus, approximately one-third of all
references obtained to date, deal in some way with the reactions
of 502 with carbon. .
The Reinluft G.m.b.H. has several patents describing
the use of a carbonaceous adsorbent for removing 502 from gases.
(534, 535~ 536, 537, 538). They suggest the introduction of
ammonia into the carbon to aid reaction with the sulfur dioxide.
This is only one of a series of ideas in patents which have been
granted to various companies to improve the adsorption characteristics
. of carbon. Other materials that have been added to or have been
impregnated on the carbon, include alkaline metal and ammonium
iodides or iodates, iodine itself, and various promoters, such
as manganese, copper, magnesium, iron, zinc, nickel, cobalt,
chromium, vanadium, molybdenum, tin, and their respective oxides
(U.5. Patent 3,318,662). It has been reported also that activated
carbon impregnated with an alkaline material has better 502
adsorption characteristics if it is also impregnated with a humectant.
(U.5. Pat. 3,396,122). This would suggest that moisture improves
the adsorptivity of carbon but liquid humectants, such as the glycol
or polyvinyl alcohol specified in the reference cited, would
probably evaporate or be swept off the carbon by the high temperature
flue gas.
J. 5iedlewski has investigated in great detail the
effect of the properties of activated carbons on their use as an
adsorbent for 502 (329 thru 345). He indicated that free radicals
have no influence on the physical adsorption of 502 but are active
centers for its chemisorption. He claimed that adsorbed H25
prevents the contact of free carbon radicals with oxygen. From
studies on the role of free carbon radicals in the oxidation of
502 to 503, he found a correlation between chemisorption and free
radical concentration. This reaction is promoted by carbon.
50mewhat surprisingly, 5iedlewski reported that covering the
surface of carbon with sulfur did not reduce the possibility of
oxidation of 502 to 503. Instead, the reverse might actually occur.
The thermodynamics of various reactions by which
sulfuric acid and 503 may be removed from carbon, were checked
by the computer and the potential carbon regeneration reactions
'having a favorable Log K are shown in Table IX. Reaction 3 is
believed to be the main reaction that occurs during regeneration
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of the Reinluft process and the reaction most responsible for
the degradation of the carbon. Reaction 4, although thermodynamically
favorable, is reported to occur to a much smaller extent. It
should be noted that of the seven reactions listed in Table IX,
four employing hydrogen or CO as a reductant have favorable
thermodynamic properties. This reinforces the belief that it
should be possible to regenerate carbons that have adsorbed S02
without having the carbon react with either S02 or sulfuric acid
that forms on the carbon surface or in its pores. The action
of S02 and carbon is discussed in greater detail on page 42 of
this report.
TABLE IX
CARBON REGENERATION REACTIONS
HAVING FAVORABLE LOG K
H2S0l1 + CO = H20 + S02 + C02 (1)
H2S04 + H2 = 2H20 + S02 ( 2)
2H2S011 + C = 2H20 + 2S02 + C02 ( 3)
H2S011 + C = H20 + S02 + CO (4)
S03 + C = S02 + CO (5)
S03 + CO = S02 + C02 ( 6)
SO 3 + H2 = S02 + H20 ( 7)
The most recent information indicates that the
Reinluft process has been abandoned because the carbon used to
adsorb the S02 became pyrophoric after repeated adsorption-desorption
cycles. The sorption of S02 on active carbon is not a simple
adsorption. Instead, the S02 is probably oxidized by the surface
oxides to S03 and the S03 reacts with water present in flue gas
to form sulfuric acid which collects in the pores of the carbon.
This sulfuric acid cannot be removed thermally without causing a
considerable amount of reaction between the sulfuric acid and the
carbon. The result is that the carbon surface area gradually
increases during repeated regenerations and the carbon becomes
,pyrophoric. The pyrophoricity arises from the fact that the
residual carbon skeleton is too small to conduct the heat of
adsorption from the surface, and as a result, a build up of heat
occurs within the carbon bed, leading to burning of the carbon.
Carbon is basically an ideal adsorbent for S02.
It adsorbs S02 from dilute streams, it is inert to S02, S03 and'
sulfuric acid at ambient temperatures and it can be prepared at
relatively low cost. Since the main objection to the use of
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carbon is in the regeneration which leads to its destruction, it
has been suggested that work be done to study the regeneration
of carbon. This work will involve trying to make use of those
reactions which were shown in Table IX to remove the sulfuric
acid without attacking the carbon and leading to its ultimate
destruction.
H.
Oxides of Non-Metals
The only oxide of a non-metal having significant 502
adsorption properties is silica; Silica gel has been studied
extensively as an adsorbant for S02 because of two very desirable
properties. It adsorbs 502 reversibly and is not affected by any
sulfuric acid that accumulates in the pores. Adsorption of S02
on silica gel is aided by increased surface area of the gel (239,
241, 270). One drawback to the use of silica gel as an 502
adsorbent is the fact that it adsorbs water as well as sulfur
dioxide; and since the concentration of water in flue gas is many
times that of sulfur dioxide, silica gel probably would not remove
S02 from flue gas effectively. However, those silica gels which
have the greatest capacity for adsorbing S02 usually contain a minimum
of about 5% of adsorbed water (270).
A fairly recent paper by Jones and Ross (174) presents
data that can be used to estimate the amount of S02 that could be
adsorbed from a flue gas. Thei~ data show silica gel to be a poor
adsorbant for S02 under flue gas conditions. These investigators
plotted the weight of 502 adsorbed per gram of silica gel vs. the
partial pressure of 502 at 323°R, the highest temperature studied.
According to their data, the amount of 502 adsorbed from a gas
having an 502 concentration similar to the 300 ppm concentration
found in flue gas is estimated to be only about 6 mg per g. To
extrapolate these data to the point where 90% of the S02 from flue
gas would be removed at 323°R, which is too low fo~ flue gas
treatmbntt 1 gram Of silica gel would be neeqed for every six-tenths
mg of 802 removed. They a~so found that heat of a~sorption of
S02 on silica gel varied from 9.3 Rcal. on fresh silica gel to
7.8 Rcal. per mole on silica gel that had a high degree of surface
coverage with S02. Thus, th~_~~at of adsorption of 502 on silica
gel is about twice the heat of condensation of 502, which is 5.1
Rcal. per mole. This indicates that adsorption of S02 on silica
gel involves something more than merely a phase change.
Although silica gel itself is not a promising adsorbent
for S02, many references claim that doped silica gel adsorbs
fairly large concentrations of 50'2. Thus, sodium oxides, vanadium,
vanadium plus tin, and many other combinations are reported to
enhance the adsorption of sulfur dioxide on silica gel. Takats
(369) studied the adsorption of S02 from S02-air mixtures using
doped silica gel containing 1, 2, 3, and 4 moles of silica (Si02)
- 38 -
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per mole of sodium oxide (NazO). He showed that the most active
compound was NazO.28i02, and that the weight percent of 802 adsorbed
on the sodium sillcate calculated as 804 reached 60.9% at 550°C
for the Na20028iOz, compound. The sodium oxide silica compound
containing a 1:1 molar ratio was the next most active. Hodek (155)
reported excellent adsorption on the use of vanadium-doped silica
gel. Vidra (421) prepared a series of silica gel containing
ferric ions and claimed that the preparations were complicated and
depended on the buffer composition. Levy (225) reported on the
interaction of 802 with iron on silica bases, including silica-
alumina. He claimed the formation of both sulfate and sulfite ions.
pevnyi (280) studied the adsorption and oxidation of 802 on silica
gels activated with chromium and tin, platinum, and with barium-
vanadium compound. All adsorbed far more 802 than undoped silica
gel. Dzis'ko (197) described the preparation of many silica gels
in detai 1.
A Russian paper (110) describes the preparation of active
silica gel adsorbants by coprecipitation followed by calcination.
Their results showed silicate formation in the 8i02-Mg(OH)z system
but gel formations in the 8iOz-Cr(OH)3 and 8i02-Fe(OH) 3 systems.
The formation of gels in these systems was attributed to mutual
stabilization caused by the respective ions which prevented
crystallization of the gels. Co-precipitated samples had higher
thermal stability of the surfaces than those prepared by mechanical
mixing.
A Netherlands patent application (551) claims a process
for using metal-doped silicas to adsorb 802 from oxygen-containing
gases. Metal doped silica-alumina and silica-magnesia are also
mentioned. . The m~tals used to dope the carriers were 5 to 15 weight
percent copper, 0.1 to 10 weight percent chromium, and 0.1 to 2
weight percent barium oxide. The patent claims that 802 is adsorbed
at 325 to 425°C, and is removed at from 350 to 450°C by passing a
reducing gas mixture containing hydrogen, carbon monoxide, methane,
ethane, propane, or butane through the catalyst bed. Other metals
mentioned as possible impregnants include alkali metals, and iron.
These metals can also be regenerated by the use of a reducing gas.
The ability of silica and doped silica gels to remove 802
and 803 from gas streams is apparently a function of gel porosity.,
According to Chufarov (43) the adsorption of 802 increased as the
porosity of the gel increased, until a maximum was reached. Then
greater porosities did not lead to greater further adsorption
of 802, presumably because of poor diffusion of 802 into the gel
structure. Kharmandar'yan (198) state that the sorptive capacity
of silica gel for 802 did not depend on total pore volume but
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rather on the differential distribution of the pore volume, and
claimed that 7.65 A radius was the most effective pore size. He
also reported that iron salts gave more active silica gel than
salts of aluminum and manganese. McGavack (239) studied different
methods of preparing silica gels and how their preparations affected
the adsorptive capacities at temperatures of from -80 to 100°C.
He reported that gels containing from 4.85 to 9.97 weight percent
of water had a maximum adsorptive capacity for S02. The water
affected the size of the pores in the gels. He also reported
that the adsorption rate for S02 decreased markedly if air was
present, but did not run tests on air containing varying amounts
of water. Ficai (117) claims that gelatinous silica has a
lower saturation value for S02 than alumina or active carbon,
but that it is superior because it is more easily activated by
high temperatures or sweeping gases and is cheaper.
The literature on silica contains a great number of
references dealing with the manufacture and properties of vanadium
on silica gels. These are used primarily to promote the oxidation
of S02 to S03 for the manufacture of sulfuric acid. The pertinence
of these references to this study is questionable. These materials
are inactive below 400°C and show maximum activity at between 450
and 500°C. This is believed to be the temperature region in which
the vanadia is in a molten or liquid form. These references might
be pertinent to two-stage oper.ation studies in which the S02 in the
flue gas would first be oxidized and then the S03 would be adsorbed.
Although their value in this investigation is doubtful, many of
these references were included in the bibliography because of possible
leads which they might furnish in allied investigations. .
Because of the promise of developing doped silica
gel which could adsorb relatively large amounts of S02 and other
oxides of sulfur, it has been recommended that doped silica gels
be included in the studies to be conducted under Phase II.
I.
Hydroxides
Several hydroxides have been mentioned for their
ability to remove sulfur oxides from gas streams. Perry (277)
reported that a ferric hydroxide gel adsorbed an amount of S02
from an S02-air mixture equal to 10.9% of its weight. Japanese
patent 11648/68 (521) mentions ferric hydroxide as being a satisfactory
adsorbent for S02 while Belgium patent 692,466 (567) states that
iron hydroxide is only one of a number of hydroxides which are
suitable for adsorbing S02. This patent claims that hydroxides
of aluminum, manganese, alkali metals and alkali earth metals are
also adsorbents for S02. Japanese patent 14712/67 (524) also
mentions the use of manganese hydroxides as an adsorbent for S02-
- 40 -
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'- ~
A Russian paper claims that magnesium hydroxide is
a reasonably good adsorbent for 502 and that its activity can be
increased markedly by hydrothermal treatment at pressures of from
5 to 20 atmospheres (288). According to this abstract, the
hydrothermal treatment increases the specific surface and porosity
of the magnesium hydroxide and causes a decrease in the effective
pore radius of the sample.
All the references described above use the hydroxide
in the dry state. However, there are many references which use
aqueous suspensions of insoluble metal hydroxides to adsorb sulfur
oxides. Hydroxides mentioned in patents as being 502 adsorbents
include magnesium hydroxide, calcium hydroxide, zinc hydroxide,
and iron hydroxide. These data are reported in British patent
708,095 (564) and 680,868 (502); and in Czechoslovakian patent,
90,701 (500). The use of an aqueous suspension of magnesium
hydroxide to adsorb 502 from sintering gases is claimed in a
Russian paper (281).
Because of ferric hydroxide's reported ability to remove
approximately 11 weight percenEof sulfur dioxide from an 502-air
mixture, work on Phase II should evaluate its use as a potential
adsorbent for 502. Ferric hydroxide is not a stable material
and is not an article of commerce. Therefore, considerable
attention will have to be given to its mode of preparation. The
preparation used by Perry (277) will be examined, as will the types
of ferric hydroxide referred to in other references. A recent
Russian patent (218,130), describes the preparation ot' an active
ferric hydroxide base catalyst for the low temperature conversion of
or tho-hydrogen to para-hydrogen (505). This process involves the
precipitation of ferric iron with sodium hydroxide at approximately
room temperature, after which the ferric hydroxide is activated
by being kept in a vacuum at 100 to 150aC. This procedure should
be tested on some samples of ferric hydroxide used in 502 adsorption
studies.
The use of an alkaline suspension of ferric hydroxide
for 802 adsorption is claimed in two patents (512, 492). The use
of an alkaline suspension would be particularly beneficial if the
i adsorption mechanism consisted of dissolving the 802 in the aqueous
medium and then having the dissolved 502 react with the insoluble
solids. The use of an alkaline suspension of a hydroxide might be
especially attractive if the alkalinity could be imparted to the
solution by the fly ash which would be removed by the scrubbing
solution. Many fly ashes are known to be basic and to contain
relatively large amounts of lime. These might yield a solution
sufficiently alkaline to aid 'the scrubbing of 502 with insoluble
hydroxides.
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SECTION III - REVIEW OF SOLID-GAS CONTACTORS
A thorough review of the literature reveals five processes
within the scope of this contract that are in either the pilot or
demonstration plant stage of development. In Appendix I detailed
process studies of each of these are developed. Presented
are flow sheets, material and energy balances, state of development,
economics, chemistry, and problem areas to the extent that this
information is available. In certain cases, some information was
inferred from limited data, and engineering judgement.
The five processes under development are:
Reinluft
Sulfacid
Hitachi
Grillo
Still
Of these, the first three employ carbon as an oxidative
sorbent. The latter two employ metal salts as sorbents. Schematic
flow sheets for each of these processes are shown in Figures 3
through 7 in Appendix II.
A.
Carbon Based Processes
Activated carbon is one of the materials widely used
as a sorbent for polar gases. The effectiveness of active carbon
as a general purpose sorbent correlates well with surface area.
There is virtually no correlation, however, between surface area
and the effectiveness of various carbons as S02 sorbents from
stack ga,ses.
Furthermore, thesorptive capacity of carbon for S02
from stack gas is several fold greater than its capacity to sorb
pure S02 at the same total pressure. Juntgen, (175 thru 180)
among others, has performed definitive studies which show that
the high capacity of carbon for S02 from stack gas is the result
of a complex series of chemical reactions which consume water
and oxygen as well as sulfur dioxide.
Sulfur dioxide is adsorbed on the surface of carbon
from the stack gas. Even at saturation, only about 0.5 to 1
percent by weight can be adsorbed by a carbon of surface area
approaching 1000 square meters per gram.- The carbon surface also
adsorbs other gases from the stack gas. Water, carbon dioxide and
oxygen are all adsorbed in competition with S02.
- 42 -
-------
Certain sites on the carbon surface hold localized
unpaired electrons. These sites, which can be detected by electron
spin resonance Spectroscopy, are active catalysts for the combination
of the sorbed sulfur dioxide with sorbed oxygen. This reaction
produces sulfur trioxide as a sorbed species. This, in turn,
reacts with sorbed (or gaseous) water to form sulfuric acid.
Even at usual stack gas temperatures, the sulfuric
acid is below its dew point. Accordingly, it forms a condensed
phase within the pore structure of the carbon. The acid is held
within the pore structure of the carbon by capillary forces.
The acid too establishes an equilibrium with the
water vapor in the stack gas. Typically, the acid sorbed within
the pore structure contains about 30 percent water by weight
(1.8 moles H20 per mole H2SO~).
In summary, carbon is functioning as an oxidation
catalyst and as an inert matrix to hold the sulfuric acid that
is formed on oxidation. Since it is not behaving as an adsorbent,
this sorption process cannot be viewed in terms of the conventional
concepts of adsorption which are usually applied to sorption of
gases on carbon and the concept of an equilibrium sorption isotherm
for 802 from stack gas on carbon is meaningless. Instead, the
process must be approached in terms of the concepts of chemical
kinetics in which saturation of the carbon is the filling-up
of the carbon with sorbed acid. The active surface of the carbon
occludes acid and so decreases the rate of sorption.
The kinetics of the overall reaction (sorption) are
interesting and important in themselves since there is a change
in the rate controlling step in the temperature range of interest.
At low temperatures, the surface is essentially saturated with 802
and oxygen, and the rate is limited by the kinetics of the 802
oxidation step. As the temperature is increased, the overall
reaction rate increases.
As the temperature is increased further, this rate
levels out~ and eventually begins to fall. ~his occurs because
the sorption of 802 on the carbon surface decreases strongly with
increasing temperature. Eventually, a point is reached at which
the sorbed 802 concentration on the surface of the carbon is so
low that it limits the rate of the overall reaction which achieves
a maximum rate at temperatures between 200 and 250oP.
The regeneration of saturated carbon is
complex process. To date, two methods have been
simplest of these is washing. Water is trickled
of saturated carbon. the water leaches the acid
also a
~sed. The
through a bed
from the carbon
- 43 -
-------
Certain sites on the carbon surface hold localized
unpaired electrons. These sites, which can be detected by electron
spin resonance Spectroscopy, are active catalysts for the combination
'of the sorbed sulfur dioxide with sorbed oxygen. This reaction
produces sulfur trioxide as a sorbed species. This, in turn,
reacts with sorbed (or gaseous) water to form sulfuric acid.
Even at usual stack gas temperatures, the sulfuric
acid is below its dew point. Accordingly, it forms a condensed
phase within the pore structure of the carbon. The acid is held
within the pore structure of the carbon by capillary forces.
The acid too establishes an equilibrium with the
water vapor in the stack gas. Typically, the acid sorbed within
the pore structure contains about 30 percent water by weight
(1.8 moles H20 per mole H2S04).
In summary, carbon is functioning as an oxidation
catalyst and as an inert matrix to hold the sulfuric acid that
is formed on oxidation. Since it is not behaving as an adsorbent,
this sorption process cannot be viewed in terms of the conventional
concepts of adsorption which are usually applied to sorption of
gases on carbon and the concept of an equilibrium sorption isotherm
for 802 from stack gas on carbon is meaningless. Instead, the
process must be approached in terms of the concepts of chemical
kinetics in which saturation of the carbon is the filling-up
of the carbon with sorbed acid. The active surface of the carbon
occludes acid and so decreases the rate of sorption.
The kinetics of the overall reaction (sorption) are
interesting and important in themselves since there is a change
in the rate controlling step in the temperature range of interest.
At low temperatures, the surface is essentially saturated with S02
and oxygen, and the rate is limited by the kinetics of the S02
oxidation step. As the temperature is increased, the overall
reaction rate increases.
As the temperature is increased further, this rate
levels out~ and eventually begins to fall. rhis occurs because
the sorption of S02 on the carbon surface decreases strongly with
increasing temperature. Eventually, a point is reached at which
the sorbed S02 concentration on the surface of the carbon is so
low that it limits the rate of the overall reaction which achieves
a maximum rate at temperatures between 200 and 2500F. .
The regeneration of saturated carbon is
complex process. To date, two methods have been
simplest of these is washing. Water is trickled
of saturated carbon. The water leaches the acid
also a
~sed. The
through a bed
from the carbon
- 43 -
-------
particles. Unfortunately, the maximum acid concentration achievable
in the leach liquor is rather low. The hydraulics of the flow
through the leaching bed seem to be the source of the problem.
At an acid concentration between ten and twenty percent, the
liquor no longer wets the carbon particles, and satisfactory
leaching rates are not attainable. Both the Hitachi and Sulfacid
processes rely on leaching for regeneration.
The second regeneration method is thermal regeneration.
The sulfuric acid saturated carbon is heated to a temperature at
which the carbon reduces the sulfuric acid forming sulfur dioxide,
carbon dioxide, and water. Chemically, the process appears fairly
complex. Again, Juntgen and co-workers have performed the most
definitive work.
The regeneration process does not proceed at a
reasonable rate below about 650°F. In the course of heating the
saturated carbon to this temperature, the sorbed acid is concentrated
to essentially pure H2S04.
It is interesting to note that the onset of the
regeneration process corresponds to the onset of the dissociation
of sulfuric acid into water and sulfur trioxide. (See Appendix
II, Table XIX.) It appears then, that the first step in
regeneration is
H2S04 ~S03 + H20
At a temperature of over 600°F, one suspects that the carbon
surface retains very little of the sulfur trioxide.
The second step appears to be the reaction of gaseous
sulfur trioxide with the carbon surface to form sulfur dioxide and
the carbon "surface oxide". This appears to be a covalently bonded
oxygen atom attached to a carbon atom on the surface which is
still bonded to the carbon matrix by a pair of covalent bonds:
The surface oxide site apparently can react further
. with a second sulfur trioxide to form carbon dioxide and sulfur
dioxide.
S03 + C
~
( ) C=O) + S02
( ') C=O) + SO 3 ~
CO2 + S02
There are several observations that support this
mechanism. Under certain conditions, it is reported that the
majority of the sulfur values can be recovered as sulfur trioxide.
This suggests that the trioxide is the initial desorbed product.
- 44 -
-------
The o~her observation is that virtually no free carbon monoxide
is produced on regeneration unless the carbon is heated to
temperatures well above 900°F.
. Such a high temperature treatment is recommended as a
treatment for the sorbent after regeneration. This is claimed
enhance the sorption activity of the char on the next sorption
cycle. There is ample evidence that excessive coverage of the
carbon surface by surface oxide makes it inactive in catalyzing
the oxidation of sulfur dioxide during sorption.
post
to
Active carbons with low ash contents lose their
activity for S02 sorption on recycling, either with leaching, or
thermal regeneration. This is attributed to surface oxide
formation. It can be avoided by adding transition metals or
iodates to the carbon. Similar problems are not always encountered
with carbons having high ash contents, perhaps because of their
natural metal content.
1.
Reinluft Process!.
The Reinluft process uses moving beds of lump char
for both sorption and regeneration. To hold pressure drop
to a minimum, the particles are one to two centimeters in diameter.
Because the particles are large, there is a major mass transfer
limitation on the rate of sorption. Solids residence times of
several hours are required to saturate the char. Ultimately, this
means that a very large volume of equipment is required. To
maintain control over the solids flow, a high multiplicity of
units is needed.
To date, the most. severe problem with the
Reinluft process has been autoi~nition of the char bads. No
problem has been encountered on startup, but after a week or so
of operation, the beds have ignited. . This appears to be the result
of activation and consumption of the char during regeneration.
As activation proceeds, the surface area (and perhaps the
specific activity of the char)' increases. The consumption of
carbon decreases the physical strength of the cha~, and its
thermal conductivity. A point is reached where the heat of
chemisorption. -- both of 802 and also of oxygen -- cannot be
effectively dissipated and eventually the temperature inside
the char lumps exceed the autoignition temperature of the
activated char. Efforts ta correct this condition by reducing
the temperature of the char recycled from the regenerator were
, '": . I
lFlow diagrams and further descriptions of each process are
presented in Appendix II.
- 45 -
-------
unsuccessful. The point of ignition apDears to have been in the
area where the regenerated char was injected.
The most recent Reinluft Pilot at Leunen appears to
have operated without ignition problems. The oxygen level in the
stack gas there -- three percent -- is significantly lower than
that in some of the earlier unsuccessful pilot plants. The
effectiveness of the Leunen "installation in removing S02 was
somewhat below design. .
It has been reported that Reinluft G.m.b.H. has
abandoned this process and has sold all rights to Bergwerke
Verbrand, a company with close ties to Bergbau-Forschung G.m.b.H.
- Essen, the German coal research institute. This is based
on a private communication and has not yet appeared in the
literature.
2.
Sulfacid Process
The Sulfacid process is under development by
Metallgesellschaft A.G. - Frankfurt (Lurgi). This process is
also sometimes referred to in the literature as the "Stratmann
process". This is the most advanced of the processes, in that
there are commercial installations in service with several years'
operating experience.
In the strictest sense, the Sulfacid process
is not a sorption process. The sorption and regeneration by
leaching occur simultaneously. Hence, the carbon "sorbent" is
really functioning only as a catalyst bed. The stack gas is
first saturated with water. Then it flows downward through a
fixed bed of active carbon one or two feet thick made up of
carbon particles about 5-6 millimeters in diameter. Water is
also sprayed over the top of the bed and is allowed to trickle
through the bed. The resulting acid is no more concentrated than
twenty percent by weight~
Lurgi proposes that this acid be contacted
with incoming hot gases to cool and partially saturate the gas
while concentrating the acid. This process modification has
yet to be demonstrated in a commercial installation.
The Sulfacid process is not particularly well
suited to large power plants.: The water requirements are very
large. About sixty pounds of water are used per pound of
sulfur dioxide recovered. Ninety-five percent of the water used
is evaporated into the stack gas. The stack plume is not only
moist, but also fairly cool. The optimal operating temperature
of the absorber bed appears to be about 140oF. The total volume
of active carbon bed required to treat the total power plant gas
is quite large.
- 46 -
-------
While the process does not lend itself to power
plant applications, it is ideally suited to sulfuric acid plant
waste gases. There the dilute acid product is no problem, since
it can be fed as part of the makeup to the primary scrubber and
the exhaust gases generally are hot enough for adiabatic saturation
with water. Hence, the only operating problem is the fairly
high water requirement." '
3. Hitachi Process
The Hitachi process uses a number of packed
carbon beds as chromatographic absorbers. When the saturation
front is about to break through one bed, it is switched to a
washing phase. When the bed is fully leached, it is dried by
passing a fraction {25%} of the incoming flue gas through it
to dry out the carbon in preparation for a second absorption cycle.
A two megawatt pilot plant was satisfactorily operated at Tokyo
Electric's Gai Plant and a larger demonstration plant is to be
constructed. The operating cycle is 60 hours long with 30 hours
of adsorption, 10 hours of washing and 20 hours of drying. In
the preferred method of practice, the washing operation is carried
out countercurrently. A nearly exhausted tower is washed with
incoming water while a tower just off of the sorption cycle is
washed with leach liquor from other towers. P-,cid concentr'ation
is still limiteato 20 percent, however.
Because packed beds are used, the carbon
particles must be fairly large {1/2 to 1 inch} to hold the pressure
drop down. Diffusion into the carbon particles then limits the
rate of adsorption. Large inventories of carbon are required,
and therefore bulky equipment must be used. The chromatographic
mode of operation further dictates that a large fraction of the
carbon is performing no useful function at any given instant.
The towers must be constructed of acid resistant materials, and
extensive duct and damper systems are required to route the gas
to the various towers.
B.
Non-Carbon Processes
1.
Grillo Process
The Grillo process is being developed by A.G. fur
Zinkindustrie vorm Wilhelm Grillo. Their interest is primarily
in the treatment of waste gases from their smelters and acid plants.
In this context, the process makes good sense since the equipment
is normally a part of the smelter operation. For power plant
applications, the complexity of the operation and the number of
process steps involved would seem to rule this process out.
- 47 -
-------
The sorbent is a mixture of an alkaline earth
hydroxide and a transition metal (higher oxidation state) oxide.
The preferred sorbent is'magnesium hydroxide and manganese dioxide.
Sorption occurs in a spray drier into which a slurry of the
absorbent is sprayed. Two spray driers in series are used on
the gas side. The sorbent is recycled extensively within each
drier (dry sorbent is reslurried and returned to process). A
small portion of the sorbent is moved countercurrent to the gas
each cycle. The spent sorbent, containing about 40 percent
sulfur dioxide by weight, is regenerated by a reductive roasting
followed by quenching, clarification to remove dust and ash,
filtration, and drying.
The purified flue gas leaves the process saturated
with water at 120of. Reheat of this gas would almost certainly be
required. The wat~r consumption would be at least 50 pounds per
pound of sulfur dioxide removed. This estimate includes only
losses to the waste gas.' Even assuming that water is readily
available, there would be a cost of at least 20C per ton of coal
burned for power" just to provide the process water.
To summarize, the Grillo process simply does
not seem to lend itself well to power plant applications. The
problems are in both sorption and regeneration, but probably the
greatest problem is regeneration which is a chemically complex
series of a number of process steps. While the utility industry
may reluctantly accept an automated two step process as a
necessary evil, it is questionable that they would consider a six
step process.
In criticizing the process, it is important not
to lose sight of its two desirable aspects. One is the high capacity
sorbent (40% by weight S02) and the other is the use of dispersed
solid contactors. '
2.
Still Process
Germany's Firma Karl Still is developing a process
which uses the fly ashes from the combustion of certain lignites
as sorbents. The ashes which prove active are rich in calcium and
sodium and they also contain significant quantities of transition
metal oxides. Only the ashes which have been hydrated to produce
alkalai and alkaline earth hydroxides are active.
In the ,Still pilot plant, the sorbent contacts
the stack gases in a series of three transport contactors. The
solids are mixed with the gas, conveyed with it through an inverted
"U", and are collected in a cyclone. Most of the solids are
recycled to the same contactor, but some are advanceq to preceeding
contactors.
- 48 -
-------
The solids are regenerated thermally. Regeneration is
only partial, however, Some or the sorbent is bound as sulfate which
is not regenerable. Thus, after a few cycles, the sorbent is spent
and must be discarded.
Unfortunately, coals which yield active ashes do not
appear to be widespread. This, of course, raises the question whether
inactive ashes can be made active. As a first attempt, Still is
supposed to have tried to use hydrated lime to start up it's pilot
plant while awaiting deliveries of ash. These preliminary results
are reported to have been discouraging. Further runs with hydrated
limes are planned, however.
The specific sorbent employed by the Still process is
not a particularly good one. It is poorly distributed geographically,
and it is rapidly consumed by the process. The engineering, however,
appears to be excellent. The multiple-stage transport contactor
should be a promising device in conjunction with other sorbents.
C.
Comparison of Existinq Processes
The five existing processes are compared in Table X on a
number of points. The first three items of comparison provide a
capsule process description, the others the bases of comparison.
1.
Costs
In this compilation, capital costs for large base load
power plants (approximately 800 megawatt), are presented in $ per kw
of installed capacity. The operating cost estimates are in mills
per kwh. By-product credits are not included in the operating
costs, and by-product processing equipment is not included in the capital.
Vendors estimates are presented in parenthesis; those not in parenthesis
are from Katell (188, 189). It is interesting to note for the Reinluft
process the wide disparity between the cost figures provided by
Reinluft G.m.b.H. and those estimated by Katell. Katell's fiqures
are nearly 50 percent higher for the capital and almost 100 percent
higher for operating cost. The greatest point of difference is sorbent
cost. Johswich estimates the sorbent at $20 per ton while Katell estimates
it at $80 per ton. The latter figure seems far more reasonable. In
a second independent estimate, Zentgraff (447) estimates capital and
operating costs still higher than Katell's.
In general, the vendors cost estimates must be regarded
as absolute minimum values. However, Lurgi figures should be fairly
accurate since they are based on operating experience. The figures
for the Still process must be regarded as highly tentative since they
do not reflect pilot-plant experience.
- 49 -
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TABLE X
COMPARISON OF PRESENT INORGANIC SOLID SORPTION PROCESSES
Process
Sorbent
Sorption mode and
sorbed species
Regeneration Mode
and Byproduct
U1
o
Capital Cost,
large plant
$/kw
(vendors est.)
Operating Cost
mills/kwh
no B.P. credit
(vendors est.)
Scale Factor
Adapt.to Existing
Plant
Stack Gas
Operability
Rein1uft
Scmicoke
Oxidative.
sorption
H2SO..
Thermal
SO~
$17.80
(12.8).
0.86
(0.44 )
0.9 to 1.0
Difficult
215°F
8% H20
Ignition problem
seems under control.
Demonstrated recov-
ery only 75%
Sulfacid
Active Carbon
Oxidative
sorption
N.A.
Washing
60-70% H2SO..
($14.50)
(0.4)
0.8 to 1.0
Difficult
<150°F
Sat.
Operating
very well
on H2SO"
tail gases
>99% recov-
ery
Hitachi
Active.Carbon
Oxidative
sorption
H2S0"
Washing
10-20% H2SO..
$10.00
0.45
0.9 to 1.0
Difficult
250°F
10% H20
Problems with
extensive duct-
ing and dampers
. Grillo
Mg(OH)2 + Mn02
Reaction
MgSO, + MnSO..
Thermal,
Reductive
S02 or S, COS, H2S
?
?
0.8 to 0.;9
Difficult
Est. 120°F
Sat.
Unknown.
Different con-
tactors being
used in pilot
Still
Lignite Ash
Reaction
CaSo,/CaSO~
Thermal
502
($5.00)
(0.5)
0.7 to 0.8
Possible if
temp. . high
enough
300°F
8% H20
Source of
absorbent
and disposal
of spent
absorbent are
problems
€redi ts for
Precipitator
Stack height
Yes
Yes
Optional
No
No
Yes
Yes?
No
No (possibly
negative)
Yes
-------
Furthermore, the operating costs will be almost completely dominated
by sorbent costs which will vary greatly from point to point.
The vendor's estimate is presumed to be based on a power plant
burning the lignite supplying the active ash.
2.
Scale Factor
The scale factor serves simply to emphasize that
the fixed bed contactors used in all three carbon processes will
require a very high multiplicity of units. Hence, there will be
no particular cost advantage for large installations. This
should not be so large a problem with dispersed phase absorbers,
such as those used in the Grillo and Still processes. This is
reflected in the lower scale factor applied to these two processes.
3.
Adaptability to Existing Plants
Of the processes considered, only the Still
process offers a reasonable possibility of installation in an
existing plant. The bed area for the three carbon based processes
is prohibitive as would be the ducting. The Grillo absorbers
- ,
might be accommodated, but the regeneration system would have to
be located off site. With the high sorption capacity of the Grillo
process, off-site regeneration might be feasible.
4.
Product Gas
The gases generated by both the Sulfacid and Grillo
processes are cool and saturated with water, and both would require
reheat before they could be discharged. Reheat costs have not been
added into the operating costs. The product gases from the other
three processes, the Hitachi, Reinluft and Still processes, could
be discharged to the atmosphere without problem.
5.
Operability
This section highlights the operating problems
of the processes. The Reinluft process has been plagued by ignition
of the sorbent bed and by low sorption efficiencies. The
literature does not report any major problems encountered in
operating the Lurgi process. Sulfur dioxide removals have been in
excess of 99 percent. The only major operating problems of the
Hitachi process have been connected with the maze of ducts and
dampers required for its practice. Of the Grillo process, the
use of an entirely different contactor in the pilot than was used
in bench scale work was reported but not accounted for. There is
sufficient information to show that the spray dryer being used in
the pilot could not have been modeled on the bench; so this
may not indicate trouble. So far as is known from available
- 51 -
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information, no operating problems have been experienced hy the
Still process, but there are certainly logistic problems of
supplying fresh sorbent and disposing of spent sorbent.
6.
Credits
In evaluating these processes in the context of
a new power plant, the question of credits for elimination of the
precipitator and for using shorter stacks arises. Credits for
elimination of the precipitator are claimed by the Reinluft
process. In the Sulfacid process, where a venturi scrubber is used
to contact the entering gases with acid, the precipit~tor can be
eliminated. This is accomplished by use of an acid clean-up
system which might be more expensive than the precipitator. The
effectiveness of tbe proposed separation step of removing the
ash from the sorbent, however, appears questionable at best.
Dust removal as a post treatment in the Grillo process is required
in any event. Thus, for this process, the question is simply
whether one or two precipitators would be required.
The possibilities of stack height reduction are
much more difficult tq assess. There are a great many degrees
of reduction of stack height. In general, we have indicated
that stack reduction is not possible in the case of the Sulfacid
and Grillo processes, which produce rather cool plumes. This
assumes that reheating is not practical.
It seems certain that any process that
credit for stack reduction must discharge a buoyant
must reduce emissions, not only of SOx, but also of
and hydrocarbons to a very low level.
takes
plume, and
NOx, fly ash,
7.
Summary
In summary, none of the five existing processes
appears to be the ideal answer for pollution control. The Sulfacid
process appears to be well suited to treating sulfuric acid tail
gases. The Grillo process appears suited to large metallurgical
smelter operations, but poorly suited to other emission sources.
The Still process appears to be a good one where active ashes are
available. .
D.
New Developments
A survey of the current, literature reveals a number of
clues to work in progress. It seems evident 'to many observers
that the fixed bed absorber is poorly suited to treating stack
gas. Sorbent particles must be large to keep pressure drop
down. Large sorbent particles react slowly because diffusion
distances inside the particle are long.
- 52 -
-------
The trend now is toward dispersed solid contactors.
~hese may be of three types:
multiple thin fluid beds
highly recycled conveyed solids systems
highly recycled raining beds
Each of these has its advantages.
The fluid beds have the advantage of being counter-
current contactors. The gas velocities are fairly low (1-5 fps)
so contacts are very brief. These devices also waste a good deal
of pressure head across the multiple grid plates.
The raining and conveyed beds both require a fairly
large contactor (1-2- seconds of gas hold-up), and both are troubled
to some extent by segregation of gas and solids. In both cases,
solids residence times, per pass, are low. This means that
solids having moderate to high sorptive capacity ( 10% S02 by
weight) must be recycled many times through the contactor.
All three of these contactors expose the sorbent to
a severe mechanical battering. In such contactors then, the
attrition resistence of the sorbent becomes very important.
Hitachi has recently patented a raining bed contactor which has
interval baffle plates to continuously remix the solids and gas,
and to slow down the rate of passage of solids through the
contactor. This contactor would be well suited to sorptive
carbons. (It is tempting to speculate that Hitachi is working on
a process using granular carbon, and a dispersed phase contactor.)
The conveyed contactor used by the Still process is
an original design that should find extensive use in processes using
sorbents other than active ashes.
Comments in recent articles by Juntgen et ale suggest
that new possibilities in the regeneration of carbon sorbents
are being explored at Bergbau-Forschung. He suggests that
they have had success in defining conditions where sulfuric acid
will dissociate to form sulfur trioxide and water, but where most
of the sulfur trioxide can be recovered without reduction.
Unfortunately, this can probably be done only at low S03 partial
pressures and, for this reason, it may not be commercially useful.
The other process possibility is that of reducing
sorbed sulfuric acid to 802 with gaseous reductants -rather than
with carbon. Juntgen hints that Bergbau is following up on this.
The idea appears so promising that we recommend work in the
U.S. on this regeneration concept. (See above.)
- 53 -
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The possibility of a non-destructive process using a
carbon sorbent is appealing, but it may not be possible to find
conditions coupling a satisfactory rate of reaction with the
selectivity desired.
Carbon is such a popular sorbent because its mode of
sorption leads to an inherently high capacity limited only by
the porosity of the carbonaceous mass. The disadvantage of this
process is the fact that the carbon degrades on regeneration, or
produces a relatively low-valued by-product. The preceeding
discussion has focused on two possible means of circumventing
the degradation problem. A third way is to substitute some
other porous material which is inert to sulfuric acid for carbon.
Within this matrix material a suitable catalyst for S02 oxidation
at stack gas temperatures should be deposited. The catalyst
material would preferably, but not necessarily, be soluble, in
sulfuric acid. Should the material be acid soluble, no loss would
be expected since the acid solution would be retained within the
porous matrix of the support. For the support matrix, we suggest
silica in the form of silica gel.
The regeneration of such a sorbent could be either
thermal, with the production of S03 and water vapor at 700 to
900°F, or reductive, with the production of S02. Leaching might
also be a possible means of acid recovery, and higher acid
concentrations might be possible with a more hydrophylic sorbent.
Leaching could not be used if the oxidation catalyst is at all
acid soluble. We recommend that a search be made for suitable
catalystic materials to make a silica sorption process a reality.
An SOx removal process in this classification is
the subject of a recent patent issued to Juntgen (468) and
assigned to Bergwerke-Verband. The process scheme is shown in
Figure 2, page 55 . Dust is removed from the stack gas in a
high temperature precipitator. The gases then pass through a
vanadium pentoxide bed at about 800°F. Thereafter, they are
cooled in the air preheate~ of the plant to 300 to 400°F. The
gases then pass through a moving bed absorber, where the sulfuric
acid mist is sorbed onto coke. The coke may be regenerated by
washing or by a thermal-reductive process, as in Reinluft.
This process would seem to offer no particular advantages
over either the "Pennelec" (catalytic oxidation) or Reinluft
processes, and indeed serves to combine the worst of both. It
is included here solely for completeness.
- 54 -
-------
U1
U1
- . )
,}
\,
, .
800°F
WASTE
GAS
DUST
REMOVAL
. Figure 2
Bergwerke-verband 802 Removal Process
AIR
ATALYS
BED "
AIR
PREHEATER
TO
STACK
ADSORB
AMMONIACAL
LI QUOR
TO (NH4)2S04
RECo'VERY
-------
E.
Process Economics
The process economics presented in Table X and in
Appendix III are strongly influenced by sorbent costs. This is
true of both capital and operating costs. As we have mentioned
earlier, the greatest disparity between Reinluft's estimate
($12.80 per installed kw, 0.44 mills per kwh) and Katell's
estimate for the Reinluft process ($17.80 per kw 0.86 mills per kwh)
is in the cost of sorbent. This influences capital through
sorbent inventory, as well as operating cost through sorbent
consumption. Sorbent costs are important in the Alkalyzed Alumina
Process as in virtually all of the inorganic solid-gas processes.
In all these, process variables such as sorbent attrition, che~ical
degradation of sorbent, and sorbent capacity are required to
provide more than rough order of magnitude costs.
The literature search, on sorption by inorganic solids
has shown a considerable need for more base information. Data
indicating sorption under anything approximating stack gas
conditions have been- rare enough. Virtually no data on attrition
and sbrbent degradation have been encountered on any sorbent
other than carbon. Hence, it is not really possible to estimate
even hypothetical costs with sufficient accuracy to justify the
exercise. We can, however, use process economics to indicate the
economically sensitive areas so that preliminary process studies
can be concentrated there.
The sorbent cost may vary over several orders of
magnitude. Minerals may be mined and crushed to produce crude
sorbent for well under $5.00 per ton. Minerals or waste materials,
processed through fairly large plants, could run as much as $20
per ton in granular form. At the other end of the cost scale,
one can easily propose sorbents that would cost well over $100
per ton.
Processes with expensive sorbents must have very low
sorbent losses and very small capacity losses on processing.
Processes with very inexpensive sorbents can operate with high
losses, but under such circumstances, sorbent disposal may become
a severe problem. Such is the case for the limestone scrubbing
processes.
Sorbent capacity interacts strongly with the complexity
and cost of the regeneration process. A very high capacity
sorbent (40-50% by wt. S02) can carry Brelatively high unit
regeneration cost. A low capacity sorbent «3% S02) must have
a simple, inexpensive regeneration process. Quite obviously,
there is a wide range in between.
- 56 -
-------
/
/
/
The type of contactor used is an important economic
variable. In this area, we have performed some economic analysis.
As was pointed out earlier, we feel that the dispersed phase
contactor is most desirable if attrition losses can be held low
enough. To hold attrition to reasonable levels, one approach is
to reduce the kinetic ener~y of the particles. This greatly
decreases impact forces. As one goes to smaller and smaller
particles, however, mass transfer becomes limiting since the
relative velocities between solids and gas also decrease. Solids
recovery becomes a more severe problem with decreasing particle
size also. In general, sorbent particles in the 1 to 0.1 mm
range represent a reasonable compromise. Such particles have
terminal velocities in the range of 3 to 10 feet per second, and
can be readily recovered in cen1;:rifugi:il'. I~eparators. Fragments
from these particles are large enough to'be recovered in cyclones.
If it is assumed that the sorption is diffusion controlled,
then in a five second contact time, with particles of the above
size range, over ninety percent of the sulfur dioxide can be removed.
This contact time can be achieved in a 125 foot high inverted "Un
column, or in a 250 feet hiqh rainina bed column with a 40 foot per
second gas velocity, and a solids loading of one pound per 40 cu. ft.
of reactor. This is a reasonable solids loading for such a system.
The pressure would be under 5" of water for the raining bed system,
and less for the conveyed solids system.
While the gas could be desulfurized to a satisfactory
level in this system,. the sorbent would pick up only about 0.005
pounds of S02 per pound per pass. Thus, about 25 passes would
be necessary to saturate the sorbent if it were carbon.
For an 800 mw power plant, a stack about 35 feet in
diameter would be adequate. For such a system, we estimate the
following costs:
Installed Costs
Installed Equipment
$ 360M
$ 300M
$ 60M
$ 35M
$ 755M
Contactor
Cyclone Separators
Surge Bins
Draft Fan Drive 5" H20
Piping & Ducting
Instruments
Engineering
40%
20%
30%
90%
Total Cost
Contingency
Total Cost
15%
$ 685M
$1440M
$ 212M
$1652M
- 57 -
-------
The erected contactor costs are based on analogy with steel stack
costs (1,2). The remaining costs were based on Dryden and Winfield
(3) and Vilbrandt and Dryden (4).
This, we feel, is a reasonable estimate for the capital
costs of the adsorber including the draft fan. The power
consumption by the driver for the booster fan is estimated at
about 500 kw of power (Chilton).
(1)
Stankiewicz, E.J., "How To Estimate Stock Costs"
Chemical Engineering, June 1955
(2 )
Chilton, C.H., "Cost Engineering in the Process Industries"
McGraw;..Hill Book Co., Inc. 1960
(3)
Dryden, C.E., and Winfield, M.D., "Chemical Engineering Costs"
Special Report 29 - Engineering Experiment Station, Ohio State
University, Columbus, Ohio 1963
(4 )
Dryden, C.E., and Vilbrandt, F.C., "Chemical Engineering Plant
Design", 4th Ed. McGraw-Hill Book Co., Inc. 1959
- 58 -
-------
SECTION IV - THERMODYNAMICS OF SULFUR DIOXIDE SORPTION
The thermochemistry of a number of potential S02 sorption
reactions was calculated for a wide variety of common elements.
A list of potential S02 sorption reactions was formulated. Thermo-
chemical data, specifically
Enthalpy of Formation at 298.15°K from the elements,
Absolute Entropy of Formation at 298.15°C.,
Heat capacity equations, or alternatively, heat
capacity data to which an equation could be fitted,
were then sought. In so far as possible, data were taken from
the Tracor, Incorporated, under Contract PH-86-68-68. Table XI
shows the data that were collected on metal compounds and the
source of each item of data. The data themselves are tabulated
in Appendix II. In addition to the data on metal compounds,
data were assembled on a number of non-metal compounds that were
involved in the postulated chemical reactions. These data too
are listed in Appendix II.
Where heat capacity equations were fitted to heat capacity
data, a four constant form of equation was used. This form of
equation was chosen because computer studies indicated that the
fit was as good as or better than that attained with three constant
equations.
In general, .thefour constant equation was superior for
the case of gases containing four or more atoms. For simpler
gases and solids, the fourth constant had no effect on the correlation
The Cp equation used throughout was
C (T) =
P
a + bT + cT2 + d/T2
By integration of this equation, closed expressions for enthalpy
and entrophy were obtained.
a(T-TO) + £(T2_T02)
2
-d(l/T - 1/TO)2
S(T) = So + a In(T/TO) + b(T-To) + ~(T2_T02)
Hf(T) = Hfo +
+ £(T3_T03)
3
- d(1/T2-I/T02)
. 2
- 59 -
-------
TABLE .XI
'SOURCES OF THERMODYNAMIC DATA FOR METAL SALTS
= SO = = CO = Si03 = P04-
= - = S2 .S04
MET 0 OH S 3 3
H S Cp H S Cp .H S Cp H S Cp H S Cp H S Cp H S Cp H S Cp H S Cp H S Cp
LO+ T T T T T T L L .L T T T T T T T T T L L
J.+
Na T T T T T T L L L L L K L T T T T T T T T T L L L L L
KT TT- T T T T N L N L N TT T T T T T T T
... T T T T T T L L L T T T T T T T T T T T T L L L L L
Mg+
Ca+. T T T T T T L L L L L L T T T T T T TT T L L L L L L
Ba T T T T T T L K N T T T T T T T T T N N
Cr+3 T T T T T T N
~ Mo+4 T T T L L L L L L
0 - +6 T T T L L
Mn+2 T T T T T T L L T T T T T T T T T T T T LL L N
Mn+3 T T T N T T T
Fe+2 T T T T T T L L T T T T T T T T T T T T L L K N
+3 T T T N T T T T T T T T T
Co+2 T T T T T T N NMN T T T T T T
Co+3 N N
Ni+2 T T T T T T L L L L L T T T T T T
Cu+l T T T T.T T T T T T T T T.T T T T T
+2 . T T T N L L K T T T T T T T T T
Zn+2 T TT T T T L L N T T T T T T T T T T T T L L
I. Sn+2 T T T T T T B B T T T
I +4 B B K B T T T T T T T T T T T T
Key:
T = tracor Data Base B = NBS TN270-2
L = Landolt-Bornstein K = U.S. Bu. Mines Circ. 584
., Tabellen M = U.S. Bu. Mines Circ. 406
N = NBS Circular 500
-------
Phase transitions were handled, where necessary, by treating the
new phase as a separate compound. In general, because the program
was essentially a screening program, it was decided not to be
concerned excessively with solid-solid phase transitions except
where the reaction in question was on the edge of thermodynamic
feasibility.
From the enthalpy and entrophy data, free energies of
formation were calculated. These were summed to calculate the
free energies of reaction. From the free energy of reaction the
equilibrium constant was calculated.
Ff(T)
!::.F (T)
r
!::.F (T)
r
""RT
= H(T) - T 5(T)
= E.v.F. (T)
1 1 1f
= ln K
a
These computations were all carried out with the aid
of a digital computer. The programs used are labeled Computer
Programs III and IV in Appendix III at the end of this report.
1.
Results of Thermochemical Screening
The tables resulting from the thermochemical calculations
are presented in Appendix III, Tables XVIII through XLVI. The
significance of the computations of course varies from computation
to computation. The eight standard reactions that were investigated
for all cases for which the data were available together with the
expression for the K are shown in Table XII.
p
TABLE XII
Standard Metal Compound Reaction Classes
I Class
No. Reaction Kp
I
I I M C03 + 502 -+ P IP
+ M S03 + CO2
-+ co 2 so 2
II M (OH) 2 + 502 + M 503 + H20 P IP
M "SiO 3 -+ H20 S02
III + S02 + M S03 + Si02 liP
-+ S02
IV M C03 + 1/2 02 + 502 + M SO,+ + C02 P IP ./p
co 2 so 2 02
V M (OH) 2 + 1/2 02 + S02 -+ M 50,+ + H20 P IP ./p
+ H20 S02 02
VI M 5i03 + 1/2 02 + S02 -+ ,M SO,+ + 5i02 l/P '/P
+ S02 02
VII M 5 + 2502 -+ M SO,+ + 52 ps2/P(s02)2
+ 3
VIII 2MS + 502 -+ 2MO +
+ 2"52' pl. 5 IP
S2 S02
- 61 -
-------
Reaction classes I through III are simple acid replacement
reactions; classes IV through VI are oxidative acid replacements.
Reaction classes VII and VIII redox reactions in which the oxidation
state of sulfur changes. Class VIII is the "modified" Claus reaction.
Since the expression of Kp is different for each reaction,
the value of K required for the reaction to be thermodynamically
feasible also varies. The values of Kp(minimum)which must be
exceeded for reactions of each class to be feasible in a typical
power plant stack gas to produce an effluent 502 concentration of 300
ppm are shown in Table XIII.
TABLE XIII
Minimum Values of Kp for Thermodynamic Feasibility
Accepting S02 From Power Plant Stack Gas
Effluent
S02
H20
C02
02
N2
Stack
Gas Composition:
0.3 mole %
7 mole %
14 mole %
3 mole %
Balance
Reaction.Class
Kp Formulation
Kp(Min.)
I
P /P
co 2 so 2
470
II
P /P
H20 S02
1 /P
S02
P /P .102
CO2 S02
PH20/Ps02.102
1 /P so 2' 102
235
3333
III
IV
2700
1350
19200
V
VI
The criteria cited are, of course, specific to the effluent
gas in question. If the concentration of any of the species is
changed appreciably, the Kp (min.) for some, or all of the reactions
changes accordingly.
- 62 -
-------
1___-
Those reaction classes in which sulfur is a product species
(VII and VIII) are not handled so simply. For convenience, the
thermodynamics of these reactions have been calculated in terms
of the molecular species 82. Unfortunately, 82 is not the dominant
sulfur species except at the top of the temperature range of
interest, i.e., near 1000oK.
The standard state of sulfur in the range of interest
is defined as pure condensed sulfur under its normal vapor
pressure. From 298 to 393°K, this is solid rh~mbic sulfur
composed of 88 rings. At 393°K, the solid melts. As the temperature
of the melt increases, there is some cleavage of 88 rings with
the subsequent formation of polymers. At still higher temperatures,
the polymers degrade to short chains. These occur in equilibrium
with 88 and 86 rings.
The vapor in equilibrium with the sulfur melt is 88
at low temperatures. At higher temperatures mixtures of 88 and
Ss predominate. At temperatures approaching 1000ok, 82 becomes
the dominant species.
If 82 were a stable gaseous species, then the correct
values of KVII (min.) and KVIII (min.) would be 3333 and 0.547
respectively. 8ince 82 is a hypothetical state, we must add to
the free energy of reaction, the free energy of forming the.
stable form of sulfur from 82. The corrected minimum values of
KVII and KVIII are presented in Table XIV. These are computed
as KVII (min.)* Ks. 8ince the numbers cover several orders of
magnitude,- they ar~ reported as logarithms (base ten).
TABLE XIV
Minimum LoglOKp's for Reaction Classes VII and VIII
TOK
500
600 -
700
800
900
1000
loglOKpVII
-0.6707
+1.3666
+2.7798
+3.8124
+4.5952
+5.2054
10glOKpVIII
-8.0516
-4.9957
-2.8759
-1.3270
-0.1528
+0.7625
- 63 -
-------
The ranges of thermodynamic feasibility for the
reactions studied are shown in Table XV. For each metal ion,
listed in that table, there is a box which contains a + for the
reaction if it is favorable from 298.15 to lOOooK, a minus if
the reaction is unfavorable over that same range, or a specific
temperature range in which the reaction is thermodynamically favored
(e.g.<975). It must be appreciated that the ranges indicated
are only approximate since the data for many of the compounds are
of relatively low accuracy. This is particularly true of the
hydroxides and sulfides. A significant number of the fundamental
thermodynamic parameters are estimated rather than measured values.
For this reason, we did not build into the thermodynamic
computational program the sophistication to accommodate phase
transitions. The data presented in Table XV are generally based
on room temperature phases. Including the solid-solid transitions
would introduce some relatively minor changes in the table.
It must also be realized that a table of this sort
is specific to one effluent gas. Changes in the composition with
respect to sulfur dioxide, water, carbon dioxide or oxygen would
alter the table. Similarly, a change in the total pressure of
the systems would result in alteration of the table. For this
reason, the tabulation of Kp values in Appendix II should be
regarded as the primary source of evaluation data. A check should
also be made of the data files in Appendix II to determine if
there is a solid-solid phase change in the temperature range of
interest.
It is interesting to note that of 81 reactions on
which computations were made, only' 14 were catagorically unfavorable
over the range of interest. This is not to say that all of the
other 67 reactions are good candidates for S02 sorption. In
some, the reactants or products are not themselves stable at the
given temperatures and gas mixture compositions. For example,
each of the carbonates and hydroxides is in equilibrium with the
gas. For each of them, there is a temperature above which they
will dissociate to the oxide and either CO2 or water. The same
can be said for product species such as sulfite and sulfate.
Certain of the reactants are hygroscopic. Sodium
hydroxide would sorb water strongly from the stack gas at
temperatures near the boiling point of water.
The two sulfide reactions, Class VII and VIII,
quite obviously yield non-equilibrium states, if there is any
oxygen in the gas phase. Oxidation of the S8 and S6 ring is
a very slow reaction, however. Hence, at temperatures below
say 700oK, it may be possible to carry out these reactions
without oxidizing the product sulfur to form more S02'
- 64 -
-------
TABLE XV
Range of Thermodynamic Feasibility of Various Reactions
From 298°K - IOOooK for Typical Stack Gas Composition
Class
Metal
Li <900oK + 0 + + 0 0 0
Na + + <650oK + + <950oK <850oK
K + 0 0 + 0 0 0 0
Mg <375°K <450 + + <850 <750 +
Ca <575 + <600 + + <950 <750 0
Ba + + 0 + + 0 0 0
Mn+2 <425 0 <575 + 0 <950 <550
Mn+3 <550 0 0 + 0 0 0 0
Fe+2 <375 0 <425 + 0 <875 <425
Fe+3 <475 0 0 + 0 0 0 0
Co+2 <775 0 0 + 0 0 +
Ni+2 0 0 0 0 0 0 <500
Cu+2 <575 0 0 + 0 0
Cu+l <475 0 0 <750oK 0 0
Zn + 0 0 + 0 0
Sn+2 0 0 0 0 0 0 0
Sn+4 <375 0 0 + 0 0 <8250K
Key
+
o
=
Favorable at all Temp.
No data.
Unfavorable at all Temps.
entries indicate ranges of
favorable values
=
=
Other
- 65 -
-------
The tables of Appendix II are but the first step in
the thermodynamic characterization of any single reaction system.
Once a specific reactant system has been selected
for study, it should be subject to further thermodynamic analysis
of the stability of the several reactants and products. The
thermodynamics of possible side reactions should likewise be
examined if the necessary fundamental data are available.
OTHER REACTIONS
Where the metal atoms involved in reactions have
valence states additional reactions become possible.
reactions in which the oxidation state of both sulfur
metal are changed.
multiple
These are
and the
Of the systems studied, sufficient data to explore the
feasibility of such reactions was found for only the compounds
of manganese, iron, and copper.
Of the seven reactions of this type studied, all were
unconditionally favorable over the entire temperature range (for
the stack gas composition used in Table XIII).
The reactions of the iron system give a suitable example.
The three reactions studied were:
Fez (C03) 3
Fe z (CO 3) 3
Fez (S04) 3
+ 2S0z + FeSOz + FeS03 + 3COz
+-
+
+ 2SQz + 1/2 Oz +- 2FeS04 + 3COz
+ 2FeO + SOz t 4FeS03
One can, of course propose a large number of such reactions
if oxygen is included as a possible reactant. The number of
reactions which can be formulated which do not involve outside
oxygen is much small~:r::.',' Where the reactant ferric salt is
other than the hydroxide or oxide, there are problems in finding
reactions which do not involve outside oxygen and in which the
oxygen balance is preserved. It is for this reason that sulfite
species are postulated as products in the proposed reactions.
Since these reactions are thermodynamically favorable, overall +6
reactions resulting from oxidation of some or all of the S+4 to S
will be still more favorable.
- 66 -
-------
SECTION V
BIBLIOGRAPHY
The bibliography listing is alphabetical by author. Numbers
in right hand columns refer to McBee card abstract numbers
as described in Section I.
- 67 -
-------
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STAUB,
448
ZHAVORONKOVA K N, BORESKOV G
COPPER-NICKEL ALLOYS TOWARDS
AKAO. NAVK 5.S.S.R. 177 (5),
00 014 024 075 095
K, NEKIPELOV V N. THE CATALYTIC ACTIVITY OF
THE ISOTOPIC EXCHANGE OF HYDROGEN. DOKLADY
1124-7 (1967).
0426
449
AIR PREHEATER CO INC.
(?! FEB 1968).
20 081 099 091
FLUE GAS S02 REMOVAL. BRIT 1,103,B59
1102
450
SULPHUR DIOXIDE SEPARATION. FR 1,511,370
AIR PREHEATER CO INC.
(26 JAN 1968).
, 17 011 007 010 021 090 073
1103
451
AMERICAN SMELTING AND REFINING CO (HASCHE R L). SEPARATING GASES SUCH AS
SULFUR DIOXIDE FROM MIXTURES. U S 1,798,733 (31 MAR 1931).
11 031 090 078
1000
452
AMERICAN SMELTING AND REFINING CO (HASCHE R L). SULFUR DIOXIDE RECOVERY
FROM SMELTER GASES. U S 1,75B,398 (13 MAY 1930).
11 031 090 078 .
1001
- 102 -
-------
453
BABCOCK f. WILCOX CO (ROGERS C E, MATTY R E, RALSTON E
MAGNESIUM BISULPHITE PULPING LIQUOR AND ABSORPTION OF
DURING REGeNERATION. U S 3,273,961 (20 SEP 1966).
11 021 036 037 090 073
1002
L). REGENERATION OF
SULPHUR DIOXIDE
454
BARKER M E. CATALYST SUITABLE FOR OXIDIZING CARBON AND SULFUR OXIDES,
ETC. U S 1,916,249 (4 JULY 1933).
11 091 014 019 022 075
1139
455
BECKMAN J W. DESUlFURIIATIoN OF FLUE GASES. U S 2.718.453
(20 SEP 1955).
11 CI0 007 073 081
1003
456
BECKMAN J W. METHOD FOR REDUCING SULFUR COMPOUNDS FROM FLUE GASES.
U S 2,718.453 (20 SEP 1955).
11 092 007 010 073 081
1099
457
ADSORPTIVE COKE.
BELG 661,702 (16 JUL 1965).
BERGWERKSVERBAND G M B H.
13 008 090 077
BERGWERKSVERBAND G M B H.
13 008 081 077
1004
SUL PHUR OX IDES.
BELG 698.069 (6 NOV 1967).
458
1005
459
BERGWERKSVERBAND G M B H.
1. 030, 942 (25 MAY 1966).
20 008 041 027 077
DESULPHURISATION OF COMBUSTION GASES.
BR IT
1006
460
BERGWERKSVERBAND G M B H.
19671.
20 008 077
WASTE GAS TREATMENT.
BRIT 1.090,306 (8 NOV
1007
461
BERGWERKSVERBAND G M B H.
20 008 081 077
BRIT 1.095,794 (20 DEC 19671.
WASTE GASES.
1008
462
BERGWERKSVERBAND G M B H.
17 008 077
SULPHUR DIOXIDE.
FR 1,499.003 (20 OCT 1967).
1009
463
BERGWERKSVERBAND G M B H.
1968) .
17 008 025 090 077
REMOVAL OF S02 FROM SMOKE.
FR 1,528.132 (7 JUN
1010
464
FLUE GAS DESULPHURISATION METHOD. GER 1.261,266
BERGWERKSVERBAND G M B H.
(15 FEB 19(8).
18 041 008 091 081 077 090 027
1011
465
BERGWERKSVERGAND G M B ~ (GIETL W M, GROSSKINSKY 0, HUCK G, ET AL).
ADSORPTION OF SULFUR DIOXIDE FROM GASES. GER 1,04h,818 (18 DEC 1958).
18 008 077
1012
466
BERGWERKSVERBAND G ~ B H. S02-ADSORPTION-COKE. BELG 707,739
(10 JUN 1968).
13 008 090 035 029 017 096 077
1100
467
BERGWERKSVERBAND G M B H. SEPARATION OF SULFUR DIOXIDE FROM WASTE GASES.
BRIT 1,090,306 (8 NOV 19671.
20 008 090 003 018 025 035 029 077 081
1104
468
BERGWERKSVERBAND G M B H (KRUEL M, JUENTGEN H, DRATWA H).
REMOVAL FROM FLUE GASES. U S 3.345,125 (3 OCT 19(7).
11 081 008 025 012 037 049 093 090 095 077 036
SULFUR DIOXIDE
1105
- 103 -
-------
r .
469
BERGWERKSVERBAND G M B H. ADSORPTION OF SULFUR DIOXIDE AND OTHER
IMPURITIES FROM EXHAUST GASES. FR 1,495,695 (22 SEP 19671.
17 099 093 081 OOB 077 095
1118
470
BERL E. ADSORBING OXIDIZABLE GASES.
11 090 008 078 039 017 077 031
1013
U S 1,744,735 (28 JAN 19301.
471
BOEHM R, VOIGT H, SPERANSKY R, ET AL.
GASES. GER (EAST) 20,456 (9 DEC 19601.
19 OOB 014 077
1014
PURIFICATION OF EXHAUST
472
BRADLEY L. SEPARATING GASES.
20 008 090 077
1015
BRIT 112,153 (21 DEC 19161.
473
BRAUNSCHWEIGISCHE KOHLEN-BERGWERKE.
GASES. GER 567,135 (14 MAR 19311.
18 072 081
REMOVING SULFUR DIOXIDE FROM FLUE
1016
474
BURKHARDT D B.
11 036 090 073
SULFUR TRIOXIDE PRUDUCTION. U S 3,362,786 (9 JAN 19681.
1017
475
CARSON G C. PREVENTING SULFUR DIOXIDE IN SMECTER GASES. U S 1,480,743
(15 JAN 19241. .
11 096
1094
476
CHEVRON RESEARCH CO.
1968).
17 014 034 024 07.3 028 013 092 075 001
S02 AND OXIDES OF NITROGEN. FR 1,523,685 (3 MAY
1018
477
CONSOLIDATED MINING
CATALYTIC REDUCTION
(11 MAY 19371.
11 096 008 093 077
AND SMELTING CO OF CANADA LTD (LEPSOE R, MILLS J RI.
OF SULFUR DIOXIDE TO SULFUR. U S 2,080,359
1019
478
CORSON G & W H INC (MINNICK L JI. CONTROLLING SMOG WITH FINELY DISPERSED
LIME. U S 2,991,014 (4 JUL 1961).
11 021 017 073
1020
479
DE JAHN F W.
(5 APR 19401.
.17 096 093
REDUCTION OF SULFUR DIOXIDE TO SULFUR. FR 854,116
1021
480
DORR-OLIVER INC (ROBERTS E JI. SULFUR DIOXIDE. U S 2,867,506
(6 JAN 19591.
11 019 036 092 073
DRACCO CORP (GIESELER G AI. APPARATUS WITH GLASS CLOTH FILTER BAGS FOR
FILTERING SULFUR OXIDES,ETC. U S 2,167,236 (25 JUL 19391.
11 032 033 030 073
1023
1022
481
482
EIDNER D. GAS COMPONENT REMOVAL BY ABSORPTION AT HIGH GAS VELOCITIES.
GER (EAST) 58,289 (20 OCT 19671.
19 090 099
1127
483
ELECTROLYTIC REFINING & SMELTING CO OF AUSTRALIA PTY LTD (MILLS A GI.
RECOVERY OF SULFUR DIOXIDE. AUSTRALIAN 164,272 (22 JUL 19551.
12 014 092 075
1024
- 104 -
-------
484
ESSO RESEARCH AND ENGINEERI~G CO (BAKER H T, WATTS R NI. ACTIVATED
CARBON. U S 2,718,505 (20 SEP 19551.
11 008 077
1025
485
ESSO RESEARCH AND ENGINEERING CO ILEWIS W K). FURNACE FLUE GAS CO~POSITION
CONTROL. U S 3,080,855 112 MAR 19631.
11 073 081
1026
486
EUSTIS F A. REMOVING SULFUR DIOXIDE FROM SMELTER OR OTHER FURNACE GASES.
U S 1,212,199 116 JAN 19171.
11 008 010 011 077 073
1091
487
FELD W. IN THE WASHING OUT OF HYDROGEN SULFIDE AND SULFUROUS ACID FROM
GASES AND VAPORS. GER 237,607 118 APR 19091.
18 043 022 019 037 073
1136
488
FERRANTE C. SULFUR FROM SULFUR DIOXIDE-CONTAINING GASES. ITAL 412,812
116 FEB 19461.
22 008 092 073 077
1086
489
FURUKAWA KOGYO K K (NAKAZONO TI.
172,814 (31 MAY 19461.
23 008 029 035 090 077'
1029
RECOVERING OF SULFUR DIOXIDE.
JAPAN
490
GARNER J B. REMOVING SULFUR DIOXIDE FROM GASES. U S 1,145,579
16 JUL 1915).
11 008 090 077 093
1092
491
GASTECHNIK G M B H.
1935) .
20 019 017
1030
REVIVIFYING GAS-PURIFER WASTE.
BRIT 433,823 121 AUG
492
REMOVING SULFUR DIOXIDE FROM FLUE GASES.
U S 2,021,548 (19
GOODEVE C F.
NO V 1935 I .
11 019 037 017 092 081
1031
493
GRACE W R & CO (TURNER G J, LEGAL C C JRI. METAL PHOSPHATE GELS AND
METHODS FOR PRODUCING SAME. U S 3,385,659 128 MAY 19681.
11 098 073 092 001 026
1131
494
HITACHI LTD.
23 099
1106
ADSORPTION COLUMN. JAPAN
67, 26, 177 (12 DEC 1967).
495
HITACHI, LTD (TAMURA Z, HISHINUMA V). DESULFURIZING INDUSTRIAL WASTE
GASES. U S 3,398,509 (27 AUG 1968).
11 008 097 081 090 077
1135
496
HODOGAYA CHEMICAL CO (YANASAWA S,ISOMURA V). SULFUR DIOXIDE. JAPAN
59 2,960 124 APR 1959).
23 008 076
1032
497
HOHMANN H. REMOVAL OF SULFUR DIOXIDE AND S03 FROM EXHAUST GASES.
GER(EASTI 55,743 (5 MAY 1967).
19 007 010 090 092 073 081
1107
498
HORII T. NICKEL MAT BY USE OF WASTE SULFUR DIOXIDE. JAPAN 56 7,254
(24 AUG 1956).
23 024 071
1033
- 105-
-------
499
HORVATH T, NAGY K, FERDINAND Z. RECOVERY OF THE S02 CONTENT OF FLUE GAS
WITH THE SIMULTANEOUS PRODUCTION OF MAGNESITE SINTER. HUNG 152,841 (22 MAY
1966).
21 021010 011 092 073 081
1034
500
HR8LICKA K. ABSORBING SULFUR DIOXIDE AND TRIOXIDE FROM INDUSTRIAL FUMES
BY THE ZINC METHOD. CZECH 90,701 (15 JUN 1959).
15 017 090 043 073
1035
501
I G FARBENINDUSTRIE A-G.
17 008 090 077
DESULFURIZING GASES. FR 846,165 (11 SEP 1939).
1028
502
IMPERIAL CHEMICAL INDUSTRIES LTD (BORGARS 0 J).
LIQUIDS. BRIT 680,868 (15 OCT 1952).
20 017 007 090 073
TREATMENT OF GASES WITH
1036
503
IMPERIAL CHEMICAL INDUSTRIES LTD (HIMSWORTH F R, DUNN J S, IMPERIAL
CHE~ICAL INDUSTRIES LTD). CALCIUM SULFATE. BRIT 454,239 (25 SEP 1936).
20 010 036 007 092 073 037
1037
504
IMPERIAL CHEMICAL INDUSTRIES LTD (LESSING RI. PURIFYING COMBUSTION GASES
CONTAINING OXIDES OF SULFUR. U S 2,080,779 (18 ~AY 1937).
11 010 073 .
1038
505
INSTITUTE OF CATALYSIS SIBERIAN OEPT ACADEMY OF SCIENCES U S S R (BUYANOV
R A, KRIVORUCHKO 0 PI. U S S R 218,130 (17 MAY 19681.
25 019 017 098
1126
506
KLIMECEK R, JARA V. ABSORBING SULFUR OIOXIDE FROM INDUSTRIAL WASTE
GASES. CZECH 106,829 (15 MAR 19631.
15 029 035 017 090 043 073
1039
507
KOGYO KAIHATSU KENKYUSHO.
(10 JAN 19681.
20 008 081 077
SULPHUR OXIDES ELIMINATION. BRIT 1,098,557
1040
508
LESSING R. WASHING COMBUSTION GASES. BRIT 416,671 (17SEP 19341.
20 007 010 017 074
1041
509
LICENTIA PATENT-VERWALTUNGS-GESELLSCHAFT M B H.
INDUSTRIAL GASES. FR 861,191 (3 FEB 19411.
17 035 010 081 073 .
REMOVING SULFUR FROM
1042
510
LINDBLAD A R. ELEMENTAL SULFUR PRODUCTION FROM SULFUR DIOXIDE-CONTAINING
GASES. U S 2,090,797 (24 AUG 1937).
11 008 035 003 093 077
1043
511
LODGE-COTTRELL LTD (LODGE-COTTRELL LTD, BOVING J 01. PURIFYING FLUE GASES.
BRIT 435,560 (23 SEP 19351.
20 007 017 010 019 092 074 081
1,044
512
LONDON POWER CO LTD. PURIFYING GASES.
14 031 030 090 093 078
FR 738,307 (8 JUN 19321.
1046
513
LUMMUS COMPANY (GUERRIERI SI. PREPARATION OF
CARBONATES FROM THE CORRESPONDING SULFATES OR
(10 SEP 1968).
11 010 036 037 096 092 073 003 029 035
1132
ALKALI METAL
SULFIDES. U S 3,401,010
- 106 -
-------
514
MCCLUSKEY S B.
17 096 008 070
REDUCING SULFURIC DIOXIDE.
FR 774.112 (30 NOV 19341.
1128
515
MCKEE R H. SEPARATING SULFUR DIOXIDE FROM GAS MIXTURES. CAN 212,540
(19 JUL 19211.
17 096 008 070
1046
516
METALLGESELLSCHAFT A-G.
1,176,101 (20 AUG 1964).
18 008 036 090 077
ADSORPTION OF SULFUR DIOXIDE FROM GASES.. GER
1047
517
METALLGESELLSCHAFT A-G (GENSECKE W, WEIDMANN H, SIECKE WI. REMOVING
SULFUR DIOXIDE FROt4 GAS MIXTURES. GER 593,383 (24 FEB 19341.
18 008 070 001 021 019 022 092
1048
518
~ETALLGESELLSCHAFT A-G (HOFFMAN K H). SULFUR AND SULFUR DIOXIDE FROM
PYRITES. GER 1,098,921 (9 FEB 19611.
18 019 036 092
1049
519
METALLGESELLSCHAFT A-G. CARBON-TYPE CATALYST FOR THE CONVERSION OF SULFUR
DIOXIDE TO SULFUR TRIOXIDE. GER 1,176,621 (27 AUG 1964).
18 008 091 077 090
1050
520
METALLGESELLSCHAFT A-G (PAULING EI. SULFUR DIOXIDE SEPARATION.
U S 3,318,662 (9 MAY 19671.
11 008 049 077 018 090 096
1097
521
MITSIJBISHI HEAVY IND LTD.. TREATING S02-CONTAINING WASTE GAS.
JAPAN 68 11,648 (16 MAY 19681.
23 019 017 073
1051
52.2
MITSUBISHI HEAVY IND LTD. TREATMENT OF SULPHUR OXIDE-CONTAINING GAS.
JAPAN 67 14,712 (17 AUG 1967).
23 022 073
1052
523
MITSUBISHI JUKOGYO KK.
596 (9 AUG 1967).
20 022 081 073
SULPHUR OXIDE CONTG. GAS TREATMENT.
BRIT 1,078,
1053
524
MITSUBISHI HEAVY IND LTD (ATSUKAWA M, NISHIt-10TO K, MIZUMOTO Y). CONTINUOUS
RECOVERY OF SULFUR DIOXIDE WITH MNOOH. JAPAN 67 14,712 117 AUG 1967).
23 0%2 017 096 081
1119
525
MITSltBISHI HEAVY IND LTD. APPARATUS FOR REMOVING SULPHUR OXIDES IN
EXHAUST GAS. JAPAN 68 2~,847 (18 SEP 1968).
23 022 017 081 099
1134
526
MITS"BISHI SHIPBUILDING f. ENGINEERING CO LTD. REMOVAL OF EFFLUENT SULFUR
DIOXIDE WITH RED SLUDGE. FR 1,350,231 (24 JAN 1964).
17 072 030 031 001 019 040
1141
527
NATIONAL LEAD CO (URBAN S F). METHOD OF DEODORIZING AIR. U S 2,956,856
(18 OCT 1960).
11 044 090 073
1054
528
NORGES GEOLOGISKE UNDERSOKELSE (AARVIK JI. CATALYST FOR THE REACTION
BETWEEN HYDROCARBONS AND SULFUR DIOXIDE FOR THE PREPARATION OF PURE
SULFUR. U S 3,369,872 (20 FEB 1968).
11 073
1055
- 107 -
-------
529
PATRICK W A. GELS, ABSORBENTS FOR GASES, CATALYTIC AGENTS. BRIT 159,508
(26 FE~ 19211.
20 030 031 098 090 019 014 024 021 006 043 022 078
1085
530
PIGACHE P. RECOVERY OF SULFUR AND SULFUR COMPOUNDS FROM GASES.
172 III JAN 19561.
20 001 014 073 075
1057
BR IT 743,
531
PIRLET G. SULFUR DIOXIDE.
17 096 010 017 070 092
FR 779,029 128 MAR 19351.
1058
532
PISARZHEVSKII L V INSTITUTE OF PHYSICAL CHEMISTRY IBUDKEVICH G B,
SLINYAKOVA I H, NEIMARK I EI. METALLIZED SILICA GELS. U S S R 218,831
(30 '4AY 19681.
25 098 031 078 030
1108
533
PRODUITS CHIMIQUES PECHINEY-SAINT-GOBAIN IlE PAGE M, BEAU R, DUCHENE JI
POROUS BODIES CONSISTING OF PARTIALLY C~YSTAllIZED SILICA. FR 1,482,867
12 JUN 19671.
17 098 030 031 090 035 037 036 078
1109
534
REINlUFT G M B H. SEPARATION AND RECOVERY OF VAPOROUS AND GASEOUS OXIDES
FROM GASES. BRIT 824,517 12 DEC 1959).
20 008 009 090 093 077
1059
535
REINLUFT G M B H (FEUSTEL K, JOHSWICH F, STRATMANN HI.
OXIDES FROM FUEL GASES. U S 2,992,065 III JUL 19611.
11 008 009 077
REMOVAL OF SULFUR
1060
536
REINLUFT G M B H (FEUSTEL K, JOHSWICH F,
RECOVERING OXIDES OF NITROGEN AND SlJLFUR
U S 2,992,895 (18 JUL 19611.
11 008 009 081 082 077
STRATMANN HI. PROCESS FOR
FROM GASEOUS MIXTURES.
1061
537
REINLUFT G M B H IJOHSWICH F). METHOD OF AND APPARATUS FOR REMOVING SULFUR
COMPOUNDS FROM GASES. U S 3,284,158 18 NOV 19661.
11 008 009 090 093 081 077
1062
538
REINlUFT G M B H.
18 008 090 077 081
FLUE GAS TReATMENT METHOD. GER 1,262,233 (7 MAR 1968).
1110
539
RESEARCH FOUNDATION FOR DEVELOPMENT OF INDUSTRIES.
OXIDES FROM FLUE GAS. BRIT 1,098,557 (10 JAN 1968).
20 008 090 099 077 091 081
1111
REMOVAL OF SULFUR
540
RESEARCH CORP (HAZEL J F, MCNABB W M, MCELROY M KI. FERRIPOLYPHOSPHATES.
U ~ 3,403,971 (1 OCT 19681.
11 026 019 090 073 017
1113
541
RICHTER G A, WIGHTMAN G F.
U S 1,469,959 19 OCT 19231.
11 010 007 021 073
SULFUR DIOXIDE FROM BURNER GASES.
1088
542
REGENERATION OF ADSORBENTS. NETH 6,614,419
RIMER MANUFG CO LTD.
119 APR 1967).
24 096 031 030 002 073 078
1121
- 108 -
-------
! .
5'.3
ROSENQVIST T. PRODUCTION OF SULFUR OXIDES ANn SULFATES FROM PYRITE. U S
2,869,999 (20 JAN 19591.
11 019 036 092
1063
544
RUHRCHEMIE A-G.
16 AUG.19631.
13 021 090 073
ELIMINATING SULFUR OXIDES IN GASES. BELG 628,092
1064
545
RUHRCHEMIE A-G. SULPHUR OXIDES REMOVAL FROM GASES.
1,261,113 115 FE8 19681.
18 021 010 073
1065
GER
546
RUHRCHEMIE A-G (ROTTIG WI. REMOVAL OF SULFUR OXIDES FROM GASES.
GER 1,261,113 115 FEB 19681.
18 021 017 010 073 092
1112
547
SANBORN H, MCMAHON
METHOD OF REMOVING
120 MAY 19131.
11 007 036 090 096
H G, OVER BURY J T, ET AL. CONTINUOUS OR CYCLICAL
SULFUROUS GASES FROM SMELTER FUMES. U S 1,062,120
098 073
1093
548
SCIENTIFIC RESEARCH INSTITUTE OF FERTILIZERS AND INSECTOFUNGICIDES.
IAMELIN A G, BARANOVA A I, MASLENNIKOVA V N). PURIFYING A GAS MIXTURE FROM
SULFUR DIOXIDE. U S S R 190,874 (14 JAN 19671.
26 029 035 003 045 031 090 030 078
1122
549
SHELL INTERNATIONALE RESEARCH MAATSHAPPIJ N V.
DIOXIDE. BRIT 1,042,088 (7 SEP 1966).
20 029 035 003 073 019 001
1066
REMOVAL OF SULPHUR
550
SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N V. REGENERATION OF A SULFUR
DIOXIDE ADSORBER MATERIAL. NETH APPL 294,858 126 APR 19651.
24 008 093 077
1067
551
SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N V. REMOVAL OF SULFUR
DIOXIDE FROM OXYGEN-CONTAINING GASES. NETH 6,410,671 (15 MAR 19661.
24 014 045 004 002 030 001 031 021 096 078
1129
552
SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ N V. REMOVAL OF SULFUR OXIDES
FROM NATURAL GAS MIXTURES. NETH 67 16,079 129 MAY 1968).
24 081 014 002 090 078
1133
553
SHELL INTERNATIONALE REASEARCH MAATSCHAPPIJ N V. REGENERATION OF AN
ADSORBER FOR SULFUR DIOXIDE. BELG 649,971 14 JAN 1965).
13 096 081
1140
554
SHELL INTERNATIONALE REASEARCH MAATSCHAPPIJ N V
REMOVAL OF SULFUR DIOXIDE FROM GAS MIXTURES AND
IN THIS PROCESS. BRIT 1,089,716 (8 NOV 1967).
20 014 045 004 002 030 001 001 021 096 078
PROCESS FOR THE
REDOX CATALYSTS FOR tJSE
1142
555
SHINAGAWA FIRE BRICK CO LTD. COLLOIDAL EARTH SYSTEM ADSORBENT.
JAPAN 67 24,309 (22 NOV 1967).
23 008 019 002 073 077
1068
556
SHIOMI T. REDUCING SULFUR DIOXIDE. U S 1,359,114 116 NOV 1920).
11 096 007 036 037
1069
- 109 -
-------
557
SEPARATING A CO~STITUENTFROM A GAS STREAM.
SIEMENS-SCHUCKERTWERKE A-G.
BRIT 1,003,419 (2 SEP 1965).
20 019
1070
558
SILICA GEL CORP. CATALYSTS. BRIT 396,712 (8 AUG 19331.
20 091 027 001 019 024 014 023 041 039 022 031 040 075 078
1071
559
SILICA GEL CORP.
(11 MAR 1924). .
20 031 030 008 039 048 001 019 078
1072
SEPARATING GASEOUS MIXTURES. BRIT 227,309
560
SOCIETE DES FORGES ET CHANTIERS DE LA MEDITERRANEE.
COMBUSTION GASES. FR 1,399,747 (21 MAY 1965).
17 090 075
1073
PURIFICATIUN OF
561
SOCIETE NATIONALE DES PETROLES D'AQUITAINE (JEAN-PIERRE R, SOLINHAC J,
MOLINET G, ET ALl. PROCESS FOR THE RECOVERY OF GASEOUS SULPHURIC COMPOUND
PRESENT IN SMALL QUANTITIES IN RESIOUAL GASES. U S 3,363,401
(16 JAN 1968).
11 002 030 090 093 073
1074
562
SPERANSKY R. UTILIZATION OF HEAT AND REMOVAL OF SULFUR DIOXIDE FROM FLUE
GASES. GER (EAST) 15,~76 (24 SEP 19581.
19 008 090 081 077
1075
563
SRBEK J, KLIMECEK R, JAEGER L. SCRUBBING SULFUR DIOXIDE FROM WASTE
GASES. CZECH 108,093 (15 AUG 1963).
15 017 092 043 073
1076
564
STANDARD OIL DEVELOPMENT CO lLOWENSTEIN-LOM
OXIDES FROM FLUE GASES AND THEIR CONVERSION
708,095 (28 APR 1954).
20 021 017 073 081
STATE SCIENTIFIC-RESEARCH INSTITUTE OF INDUSTRIAL AND
PURIFICATION (PINAEV V A, PITELINA N P, SOSEKINA G V,
OF GASES FROM SULFUR DIOXIDE. U S S R 194,777 (12 APR
25 021 037 090 073 036
W G). REMOVAL OF SULFUR
TO AMMONIUM SULFATE. BRIT
1077
565
SANITARY GAS
ET ALl. PURIFICATION
1967).
1114
566
STATENS RASTOFFLOBORATORIUM (AARVIK J, SKJERVEN 0). FERROUS SULFIDE.
BRIT 726,216 (16 MAR 1955). t
20 019 036 073 092
1123
567
STILL C. SULPHUR OXIDES. BElG 692,466 (16 JUN 19671.
13 017 081 073
1078
568
SULPHUR RECOVERY INC (HAINES H W JR). PROCESS FOR THE SELECTIIVE
ADSORPTION OF HYDROGEN SULFIDE AND ITS SUBSEQUENT CATALYTIC CONVERSION TO
ELEMENTAL SULPHUR. U S 3,144,307 (11 AUG 19641.
11 096 002 093 073
1079
569
TOA GOSEI KAGAKUKOGYO K.K (FURUFUJI I). TREATMENT OF SULFUR DIOXIDE GAS IN
FLUE GAS. JAPAN 174,880 (6 JUN 19481.
23 008 077
1087
570
SULPHUR bXIDES REMOVAL PROCESS. BRIT 1,096,342
TSUGIO TAKEUCHI.
(29 DEC 19671.
20 008 091 093 081 077 090
1080
- 110 -
-------
571
REMOVAL OF S02~ BELG 709,513 (30 MAY 19681.
U S DEPARTMENT OF INTERIOR.
13 091 041 007 026 092 073
1095
572
U S DEPARTMENT OF INTERIOR. REMOVAL OF S02. NETH 6,800,289
(19 JUL 19681.
24 081 091 041 007 026 073 092
1098
573
UDY M J. SULFUR RECOVERY. BRIT 578,136 (17 JUN 19461.
20 036 092
1081
574
UNION CARBIDE CORP (DRESHER W H, REICHARD H Fl. SULFUR TREATED
ASBESTOS. U S 3,256,106 (14 JUN 19661.
11 002 090 092 071
1082
575
UNION CARBIDE CORP (MILTON R MI. MOLECULAR SIEVE ADSORBENTS.
U S 2,882,244 (14 APR 19591.
11 002 090 073
UNION CARBIDE CORP (MILTON R MI. MOLECULAR SIEVE ADSORBENT. U S 2,882,243
(14 APR 19591.
11 002 090 073
1116
1115
576
577
UNION OIL CO OF CALIF tDOUMANI T Fl. REDUCTION OF S02 TO SAND H2S.
U S 2,361,B25 (31 OCT 19441.
11 096
1124
578
UNIVERSAL OIL PRODUCTS CO (URBAN PI. PRODUCTION OF SULFUR. U S 3,149,920
(22 SEP 19641.
11 096 001 002 030 031 093 078
1084
579
VEREINIGTE KALIWERKE SALZDETFURTH A-G (KARSTEN 0, KOCH H H, NEITZEL U
ET ALl. APPARATUS FUR REDUCING THE SULFUR OXIDES IN FLUE GASES BY THE
INTRODUCTION OF VERY FINE HYCRATEO DOLO~ITE. GER 1,260,668 (8 FEB 19681.
18 011 007 021 010 099 092 081 073
1117
580
YOUNG S W. REMOVING SULFUR DIOXIDE ANO RECOVERING FREE SULFUR FROM
SULFUROUS FUMES. U S 1, 094, 767 12~ APR 19141.
11 073 007 010 008 092
1089
- III -
-------
APPENDIX I
PROCESS REVIEWS
- 112 -
-------
SURVEY OF S02 REMOVAL PROCESSES.
INORGANIC SOLIDS
NAME: Reinluft Process
ASSIGNORS: Reinluft G. M. b. H. By F. Johswich et al.
SORPTION SECTION
Sorbent:
Temp:
H20:
°2~
C02:
S02:
Mode:
Pref. Contact:
Thermo Chern:
Eq.Sorption Data:
Kinetic Data:
REGENERATION SECTION
Temp:
Reagents:
Byproducts:
Pref Contactor:
Thermochem:
Eq. Des. Data:
Kinetic Data:
Charcoal, peat coke or semicoke, pref ~2 Cm
particles~
125°F
-------
ECON.
Several pilot and demonstration scale units have been
operated. A demonstration unit at Cologne experienced
problems with ignition of char in the absorber; a 10 mw
unit at Luenen is operating smoothly with about 26 weeks
on stream logged in one year of operation. Performance
has been slightly below design. (75% S02 removal)
Katell estimates capital cost to be $17.77 per kw for an
800 mw installation burning 3% S coal, and operating costs
to be 0.857 mills/kwh or $2.45 per ton of coal burned. .
Estimates for a 300 mw plant burning 1.5% S coal are
$20.75/kw and 1.25 mills/kwh. Costs are exclusive of
byproduct credit.
A scale exponent of 0.9 on power plant size, and 0.7 on
unit absorber size would be appropriate. The above com-
putations are based on 10 Mw units.
PROCESS DESCRIPTION
STATUS:
Sulfur dioxide is adsorbed from the stack gas onto a slowly
moving bed of walnut-sized lumps of char. The adsorbed S02
is oxidized to S03 by the catalytic action of the carbon. This
is hydrated to sulfuric acid which remains as a condensed
phase within the char. The char containing adsorbed acid
moves downward into a regenerator where it is heated to about
700.F with heated flue gas. At this temperature the sulfuric
acid dissociates to S03 and water, and the sulfur trioxide
reacts with carbon to form C02 and S02. The enriched S02
stream is fed to a sulfuric acid plant. The regenerated char
is returned to the top of the adsorber after screening to
remove fines. The process flows are shown in Figure 1.
Inventor suggests that off gas be fed to sulfuric converter,
gases be cooled and acid recovered by a precipitatQr at such
temperature that he gets 98% acid.
BALANCE
MASS
An individual 10 Mw unit would process 3 tons of char per hour,
and would produce 622# of acid per hr (100% basis).
ENERGY BALANCE - Per unit absorber @ 10 Mw
Cooling water - 10M gp hr. C.W. @ 20° rise.
Heat - 1.1 therms per hr.@ up to 700°F.
Also require driver power for the recirculation and draft blowers.
- 114 -
-------
Figure 3
REINLUFT PROCESS
@ TO STACK
220°F
ADSORB
C.w.
STACK
GAS
1
300°
290°F
HEAT
EGEN
4
C2). TO AC I D
. PLANT
7
700°F
MAKE-UP
CHAR
FINES
Basis - 100 moles stack gas
-------
1----
SURVEY OF S02 REMOVAL PROCESSES.
INORGANIC SOLIDS
"Sulfacid" Process (Pauling or Stratmann Process)
Basic patent assigned to Metallgesellschaft A.G.,
Frankfurt.
SORPTION SECTION
Sorbent:
NAME:
ASSIGNORS:
Temp:
'H 20: .
O2:
C02 :
S02 :
Mode:
Pref. Contact:
Thermo Chern.:
Eg. Sorption Data:
Kinetic Data:
REGENERATION SECTION
Byproducts:
Activated carbon impregnated with metals, iodine.
or arsenic.
100-160°F
Saturated
PO 2 <1/2 PSO 2
Any
10% down to stack gas
Oxidative sorption
Fixed bed - Concurrent
levels
downflow
Highly favorable
N.A.
Residence time in bed is 1 or more seconds
for gas. Optimum temperature is a balance
between rate and water vapor pressure.
H2S04, up to 20% conc. directly, or up to
85% with a precooler/evaporator. Incoming
gases may be cooled and saturated with water
vapor in either a countercurrent packed tower
or a venturi scrubber prior to the reactor
bed. The dilute acid product from the adsorber
is used to cool and saturate the incoming gas.
In the process, the acid is, concentrated to a
level fixed by the temperature and humidity of
the 'stack gas.
STATUS
The process has been successfully applied to the treatment of
chemical plant waste streams. A plant operating on up to
3000 scfm flue gas from an oil fired burner is performing well.
A plant to handle 30M scfm of sulfuric acid tail gas is under
construction. Small plants have operated up to 3 years. This
is the most advanced of the S02 control processes.
'ECONOMICS
Lurgi has quoted capital costs of $14.5 per kw (8000 h/a) for
a 120 Mw oil fired power station. Projected operating ,costs
are 0.4 mills/kwh. The process is well suited to small instal-
lations, but would presumably have a fairly high scale exponent,
say 0.9. Acid concentration would be a problem. If incoming
- 116 -
-------
- -----~----~~~-~-. - -~ ~- ~._~~_.._~-- -
gas is dusty, the acid would have to be dissociated and
recombined to produce a marketable byproduct. The process
is particularly well suited to sulfuric acid tail gas treatment
where there is no dust problem, and where the dilute acid may
be substituted for a portion of the water feed to the absorber.
PROCESS DESCRIPTION
Stack gas is passed through a fixed bed of active carbon at
about 160°F. The active carbon adsorbs the sulfur dioxide and
catalyzes its oxidation to S03. This in turn reacts with water
to form sulfuric acid. The acid is continuously flushed from
the bed by a stream of wash water sprayed over the top. Acid
of 10 to 20 percent concentration is produced. The activity of
the carbon is maintained by the addition of one of several
transition metals, or iodine, or arsenic. .
The incoming stack gas is cooled and the acid Goncentrated by
evaporation in a Venturi scrubber and separator. The concen-
tration of the product acid depends strongly on the inlet gas
temperature and moisture content. For a typical stack gas
entering at 300°F, 83% acid is theoretically obtainable. Figure 2
shows the basic flows of this process. Alternatively, a counter-
current tower packed with coke may be used as a cooler/evaporator.
AND ENERGY BALANCES
The balance shown above is one of many possible operating
conditions for this process. The required inlet gas temperature
is fixed by the operating temperature of the absorber. For
absorber temperatures of 130 and 120°, the required inlet gas
temperatures are 360°F and 250°F, respectively. Significantly
less water is also required, although the product acid would
probably be more dilute than the 70 wt.% shown.
COMMENTS
MASS
This process is very well suited to comparatively small waste
gas streams, such as sulfuric acid tail gas. The process is
the most advanced of those available. Operation is very simple.
The corrosion conditions are severe. The high specific water
consumption and the cold, wet plume are potential problem. areas.
Plume reheat would be required for lar~e scale installations.
- 117 -
-------
"SULPACID" PROCESS
DUST
REMOVAL
JTO
l STACK
WATER
STACK
GAS
ABSORBERS
DILUTE ACID
CONC. ACID
G) @ 0 @ (0 @)
N2 74.9 74.9 74.9
C02 14.7 14.7 14.7
H20 7.3 18.3 22.6 16.5 11. 9 0.63
02 2.8 2.8 2.67
S02 0.3 0.3 0.03
H2Sq" 0.27 0.27
T 5100P 2300P 1400P 1400P 2300P
Ewt. . 2984# 3 2 3 8.1£- 297# 240# 37.7#
In pound moles unless indicated.
Pigure4
- 118 -
-------
SURVEY OF S02 REMOVAL PROCESSES.
NAME: Hitachi Process
ASSIGNORS: Hitachi LTD.
SORPTION SECTION
Sorbent:
Temp. :
H20:
O2:
CO2 :
S02:
Mode:
Pref. Contact:
Thermo Chern:
Eq. Sorption Data:
Kinetic Data:
REGENERATION SECTION
Temp. :
Reagents:
Byproducts:
Pref. Contactor:
Eq. Des. Data:
Kinetic Data:
.INORGANIC SOLIDS
Activated carbon - not consumed - moderate
to large briquettes or particles.
~300 to 200°F inlet, 55°F lower outlet
Oil or coal flue gases are satisfactory
As Reinluft
No limits
As Reinluft
As Reinluft
Fixed bed
Highly favorable
No data - not an equilibrium
sorbed material is converted
condensed phase.
Unknown
situation since
to capillary
<212°F for wash, incoming stack temp. for
drying.
Water, air
Dilute sulfuric acid (10-20%)
Fixed beds
Only a portion of gas used to
so that effluent gas is never
with water.
Desorption is diffusion controlled, preferably
operated with several towers in a counter~
current manner.
dry the towers
fully saturated.
STATUS
A 2 Mw equivalent plant is operating at Tokyo Electric's Gai
plant. A 50 Mw unit is under design.
ECONOMICS
$lO/kw capacity @ 175 Mw, 90% removal (assume 8000 hrs)
0.45 mills/kwh exclusive of byproduct. Scale factor would
be expected to be near 1.0, say 0.9
- 119 -
-------
PROCESS DESCRIPTION
Stack gas passes first to an electrostatic precipitator where
dust is removed. Then it goes to a flow splitter where a
portion is led to a tower containing water saturated carbon.
The gas leaves the tower cool and water-saturated. Pressure
is boosted with a draft fan and the gas mixes with the rest of
the incoming gas. The combined stream at about 245°F passes
through a fixed bed of dry active carbon. The sulfur dioxide
is adsorbed, oxidized, and converted to sulfuric acid sorbed
within the carbon structure. The gas is discharged at sub-
stantially the same temperature as it entered the absorber.
When a given adsorbing tower approaches saturation, the gas
flows are diverted, and water is sprayed over the bed to wash
the sulfuric acid out of the carbon. To increase the concen-
tration of the product acid, several towers may be extracted
counter currently. Twenty percent is about the most concentrated
acid achievable with this system. A typical cycle calls for
30 hrs adsorb, 10 hrs wash, and 20 hrs dry.
ENERGY BALANCE
No net energy input is required by the process as shown, except
drives for draft fans. Steam would also be required to con-
centrate the dilute product acid in any actual installation.
COMMENTS
The Hitachi process has as its major problem the dilute byproduct
acid produced by evaporation. To have any byproduct value, this
product would have to be upgraded to ~70% acid. The concentrated
product is useful for on~y limited uses, and might require
dissociation and recombination to produce a product of saleable
value. U.S. conditions do not make such reprocessing of acid
favorable at present sulfur prices. Because of the unfavorable
scale exponent, very large process installations would have little
economic advantage.
- 120 -
-------
Figure. 5
Hitachi Process
3
TO STACK
245°F
@
-------
SURVEY OF Sel.2 REMOVAL PROCESSES.
INORGANIC SOLIDS
NAME: Grillo Process
ASSIGNORS: A.G. fur Zinkindustrie vorm Wilhelm Grillo
SORPTION SECTION
Sorbent:
Temp. :
H20:
O2 :
CO2 :
S02 :
Mode:
Pref. Contact:
Thermo Chern.:
Eq. Sorption Data:
.Kinetic Data:
REGENERATION SECTION
Temp. :
Reagents:
Byproducts:
Pref. Contactor:
Thermo Chern.:
Kinetic Data:
STATUS
Mixture of transition metal oxide and
alkaline earth hydroxide, pref Mn02 + Mg(OH)2
Presumed to be 200 to 250°F
than saturation
required
slight interference with chemistry
Less
None
Some
Any
Reaction of S03 with Mn02 and with Mg(OH)2
Gas phase, reaction presumably with Mg(OH)2
with transfer in slurry to Mn02 forming
MnSO.. . .'
Spray Tower
Highly favorable for reaction
Probable limit on the per pass S02 pickup set by
the Mg(OH)2 content.
Unknown
Unknown, presumably lSOooF
Air, coal for fuel and possibly for reductant.
High S02 stream, presumably converted to
sulfuric acid.
Multiple hearth furnace
To be established.
Unknown
Small scale pilot plant tests have been completed by'A.G. fur
Zinkindustrie vorm Wilhelm Grillo. An 8 Mw unit constructed
near Cologne and went into operation in October 1967. This is
to handle about 12,000 scfm of oil burner stack gas or sulfuric
acid tail gas. '
ECONOMICS
No economics have been published, to our knowledge, on the
process. The process conditions are not sufficiently well
known to be able to make an intelligent cost estimate. The
- 122 -
-------
number of processing steps and the number-of mechanical
operations required suggest that the process will be very
expensive unless significant breakthroughs are made.
PROCESS DESCRIPTION .
The Grillo process absorbs S02 in a mixture of a metal oxide
and an alkaline earth hydroxide [Mn02+ Mg(OH)2 is preferred].
A slurry of the absorbent is sprayed into a spray dryer where
it dries as it contacts the stack gas. The particles of
absorbent are collected, and most are reslurried and sent back
to the spray nozzle. Two spray towers are used. Fresh absorb-
ent is fed to the slurry tank of the second tower. A small
quantity of absorbent passes to the first tower each pass, and
a like amount of material is removed from the first tower for
regeneration. The loaded acceptor (~20% sulfur) is mixed with
coal, roasted to give S02 suitable for acid plant feed. The
calcine is slurried in water, passed through a clarifier where
fly ash separates as an underflow, filtered, and dried. This
is then returned to the absorbers. Figure 4 is a process flow
sheet.
BALANCE
At the moment we have insufficient information on either the
chemistry or process conditions to develop a detailed flow sheet.
We have developed a hypothetical flow sheet and mass balance,
however, which is subject to certain assumptions.
ASSUMPTIONS
MASS
The following assumptions were made in deriving the material
balances:
1:1 mole ratio Mn to Mg.
Complete conversion of Mn, 50% conversion of Mg (Bal. ash).
20% sulfur content in spent absorbent (Brocke).
Top calciner temp. is 15000F (MnS04 decomp; .temp.).
Coal provides fuel value only at 12,000 Btu/lb, 10% ash,
compo (CH)n
Gases leave the calciner at 1000°F, 10% X's air.
Solids leave calciner at 1500°F.
A 2% slurry is fed to clarifier, separation is perfect,
bottoms are 5% ash.
Filter cake is 40% solids.
Recycle slurry to dryers is 30% solids;
Mean recycle ratio for absorbers in combination is 10:1.
The roasting operation can be carried out in such a fashion
as to produce S02 directly without first completely reducing
all sulfur species to COS, S, and H2S.
- 123 -
-------
ENERGY.BALANCE
0.174 Ibs Goal per Ib SO~ are required for regeneration.
will also be a large driver requirement for' a booster fan
for machinery drives.
- 124Q-
There
and
-------
Figure
6
GRILLO PROCESS
TO
STACK
DRY
SLURRY
Basis 100# moles of stack gas
-------
SURVEY OF S02 REMOVAL PROCESSES. . INORGANIC SOLIDS
. I
NAME: Still Process
ASSIGNORS: Firma Karl Still
SORPTION SECTION
Sorbent:
Temp. :
. H20:
02 :
C02:
S02:
Mode:
Pref. Contact:
Thermo Chern.:
Kinetic Data:
Hydrated basic lignite ash (possibly
augmented or supplanted by hydrated lime).
850°F to 200°F.
Depends on temperature, >P decomp. Ca(OH)2
Any
No interference noted in literature.
Any
Reaction of calcium hydroxide with S02.
Transport bed.
Highly favorable. Temperature limited by
decomposition of Ca(OH)2.
Unknown. Reaction is probably controlled by
diffusion of gas into the reacted solid.
REGENERATION SECTION
Partial regeneration may be practiced, or spent absorbent may
be discarded.
Reagents:
Byproducts:
Pref. Contactor:
Thermo Chern.:
Kinetic Data:
STATUS
Inert gas sweep.
S02' CaSO~
Kiln or multiple hearth
Multiple favorable reaction paths, thermal
dissociation of CaS03 can go to CaO and S02,
or to CaS and CaSO~. .
Unknown.
Small scale demonstration was accomplished by Firma Karl Still.
A 10 Mw unit was to have started operation at Herne Power
Station near Recklinghausen, Germany, November, 1967.
ECONOMICS
Capital costs of $5.00/kwh and 0.5
are claimed by Still, for a 200 Mw
assigned to ash is unclear.
mills/kwh operating expense
installation. Value
PROCESS DESCRIPTION
Gases from the power plant dust collector are contacted with a
hydrated lignite ash in sequential transport contactors. The
ash is collected by cyclones and bag filters, and the off gases
- 126 -
,
-------
are led to a stack. The absorbent is regenerated by heating.
During regeneration an S02 rich stream is produced which may
be fed to a sulfuric acid plant. The absorbent is then hydrated
before being returned to the absorber.
Only the ash from lignites with a high lime content are suitable
as absorbents. Unfortunately, with repeated cycling, more and
more of the calcium in the sorbentis bound irreversibly as
calcium sulfate. Thus, the lignite ash must be inexpensive and
readily available. The flows are shown in Figure'. Efforts
will be made to operate the pilot plant with hydrated lime.
AND ENERGY BALANCE
MASS
MASS
The specific performance of the Still
dependent on the make-up of the ash.
likely to determine the quantities of
tion and regeneration.
Assuming 90% S02 removal, and based on 100 moles of entering
stack gas, the process will use 9.7* of water. The calciner will
consume about one pound of coal per ten to fifteen pounds of
solids thrbugh~ut. The magnitude of the solids purge is likely
to be considerable (say, 20-25%) under the best conditions, but.
under less favorable conditions, even more material may have. to
be purged.
BALANCE
Insufficient data are available to specify the recycle ratios
required for various absorbents. Regeneration, too, will depend
strongly on minor constituents in the ash.
ENERGY BALANCE
process will be strong~y
Minor constituents are
CaSO~ formed during absorp-
Calciner fuel is the only extraneous energy requirement.
- 127 -
-------
I-'
N
co
WASTE
GAS
DUST
REMOVAL
..... t
:-:-:-:-: ',:-:-:-:, '1' ',',',',',',','
"" 1""", ',',',',',','
:1:<:::: :' ':::::: :: : ":::::
. "0 "0"' .'.. °0'.' °0 . '..
. . . . . . . . .. .
. ... . . . . . .
. . . . . . . . . .
. '.' .... . .
. . . . . " . . . . .
. ... . . . . ., .,.
:: :::::: :::::'-:-::<:::::::: "
. . . . ..
. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
. . .. . .
. . . . .
. . . . .
. . . . .
. . . . . .
FIGURE 7
STILL
PROCESS
TO STACK
MAKE -UP LIME
WATER
HYDRATOR
CALCINER
FUEL
WASTE, SOLIDS
..
,~
-------
APPENDIX II
THERMODYNAMIC COMPUTATIONS
- 129 -
-------
TABLE
XVi
THERMODYNAMIC VALUES FOR MISCELLANEOUS COMPOUNDS
HO So A B C D
HzS04 -194.548 37.501 36.77 9. 16 -3 -2.088-6 -5.432 + 5
S03 -94.470 61. 345 9.054 1. 679-2 -7.659-6 -11. 3429+4
SOz -70.947 59.297 7.0756 1.076-3 -4.848-6 -2. 9107+ 4
Sz + 30.84 54.51 7.866 1. 892 -3 8.996-7 -2. 9053+ 4
COz -9~.035 51. 125 6.94 9.742-3 3.667-6 -5.7464+4
CO -26.416 41. 218 5.735 2.703-3 -5.356-7 4.2111+4
C 0 1. 372 -0.221 9.963-3 -4.611-6 -2. 7007+ 4
Oz 0 49.007 5. 179 5.24'-3 2.141-6 4. 186+ 4
Hz 0 31. 208 7.567 -1. 5 -3 1. 193-6 -2. 9332+ 4
ui!O -57.798 45. 105 6.954 2.569-3 3. 152-7 2.4706+4
SiOz -217.5 10.0. -5.364 5.413-2 -3.396-5 2. 57565+ 5
Note:
Positive and negative integers after values in
Columns B, C, and D are exponents of powers of
10. Thus, 9.16-3 is 9.16 x 10-3.
- 130 -
-------
UKJ
298.1::)
4010
510 iii
60£1
700
800
900
101i10
HKJ
298.15
400
500
600
700
8010
.900
1000
HKJ.
298;;1:::>
4£10
~00
600
7010
800
900
101010
TABLE XVII - REGENERATION REACTIONS
TABULATIONS OF Kp FOR VARIOUS REACTIONS
S03 = 1/2 Oz + SOz
DEL r[CALSJ LOG1f(J K
16~27.9 -12.3424
14514.~ -7.93503
12185. -~.32911
9816.83 -3.~7788
7418. -2.31736
4991.96 -1.364~4
2540.16 -.617198
62.9723 -1.377107 E-2
HZS04 = S03 + HzO
UEL F[CALSJ
21722.9
15733.2
10250.1
5135.54
356.905
-4114.37
-8301.43
-12222.6
LOG10 K
- 1 5 . 9 32 6
-8.60126
-4.48293
-1.871.71
-0111496
1.12465
2.01704
2.67282
K £Q
4. 54558 E - 1 3
1016137 £-6
4.68633 E-6
2.64317 E.;-4
4.81546 E-3
4.31976 E-2
.241436
.968789
K EQ
1.16783 E-16
2.50461 E-9
3.289104 £-5
1.34365 E-2
.173:;78
13.3246
1104.003
470.786
2HzS04 + C = 2 SOz + COz + 2 HzO
DEL H CALS )
-171S~.9
-34101.9
-501099.8
-65480.8
-810296.2
-94~97.
- 1 08428.
-12182~.
LOG10 K
12.583
18.6434
21.9114
23.86~3
25.£1843
25.8::»79
26.3453
26.640~
- 131 -
K EQ
3.82829 E 12
4.39900 Ii: 18
8.15504 E 21
7.334101 Ii: 23
1.21424 E 25
7.20881 E 2~
2.21441 E 26
4.36988 E 26
-------
HKJ
298.1~
4fOI{J
5010
.600
700
800
900
Hi00
HKJ
298.1~
400
500
6010
71010
800
91010
11000
HKJ
298.15
400
~IOIO
61010
700
8010
91010
11000
TABLE XVII (Continued)
H2S04 +
vEL. F[CAL.~J
7~60.38
- 262:> . b 3
-lC~~1ftJ.6
-21966.9
-31309.8
-410459.7
-49436.4
-::>8257.8
C = H20 + S02 + CO
L.OGIIO K K ~~
-5.54516 2.84997 E-6
1.43S~3 27.2603
5.4278:> 267824.
8.00612 1.101419 .~ 8
9.781109 6.104067 E 9
11.1O~96 1.14697 E 11
12.0118 1.102763 E 12
12.7397 5.49162 E 12
H2S04 + CO = H20 + S02 + CO2
uEL. H CAL.S J
-24716.3
-3147601
-37689.2
-43513.9
-48986.4
-54137.4
-~8991.2
-6:J567.3
L.OGIIO K
18-1282
17.21078
16.4836
15.8592
15.3032
14.7983
14.3334
13.910108
K EQ
1 .34327 t: 18
1.61371 ~ 17
3.04492 I:: 16
7.23139 t.: 15
2.1011011 Ii; 15
6.28::»07 I:: 14
2015487 E 14
7.9~735 I:: 13
HzS04 + H2 = 2 HzO + 502
vl::L. "[CAL.~J
-16084.9
-23185.5
-29748.
-35922.5
-41742.5
-47239.9
-52441.6
-573710.
L.OGI0 K
11.7975
12.6754
13.01104
13.0924
13.04102
12.9129
1 2 . 7 42
12.5455
K t:bI
6.27307 E' 11
4.73596 £:: 12
1.102435 E 13
1.23714 t: 13
1.09709 E 13
8.18299 t: 12
5.52123 E 12
3.51195 £ 12
- 132 -
-------
TABLE XVII (Continued)
S03 + C = CO + SOZ
HKJ
298.15
4010
5010
600
700
81(J0
9"''''
10010
OEl HCAlS J
-14162.5
-18359.
-22660.7
-27102.4
-31666.7
-36345.3
-41135.
-461035.2
lOG10 K
U:h3875
10.0368
9.91078
9.87783
9.89258
9.9349
9.99479
10.0669
S03 + CO = SOz + COz
HKJ
296.1~
41010
500
6"'0
71010
BI(J'"
9010
10010
DEL F[CAlSJ
-46439.2
-472169.3
-47939.2
-48649.4
-49343.3
-501023.
-50689.8
-~1344.7.
lOG10 K
34.06108
25.8091
20.9665
17.13109
15.4147
13.6737
12.3164
11.2279
K £61
2.441039 E 10
1.108640 t:: 10
8.14292 £ 9
7.54804 E 9
1.80874 E 9
8.60796 E 9
9.88081 E 9
1 . 1 6648 Ii. 10
. K EQ
1.15022 E 34
6.44293 Ii. 2:>
9.25779 E 210
5.381 91 E 1 7
2.59845 E 15
4.71691 E 13
2.07193 £ 12
1 .691023 £ 11
S03 + Hz = HzO + SOz
HK] uli.l n l;ALS J lOG1'" K K £61
298. 15 - 3 78 10 7 . 8 27.7301 5.37154 E 27
4100 -38918.1 21.2767 1.89"'89 E 21
5010 -39998. 17.4934 3.11443 E 17
61010 . -41058. 14.9641 9.210730 E 14
100 -42099.4 13.1511 1.41820 E 13
8100 -43125.5 11.7883 6.14128 E 1 1
9010 -44140.2 10.725 5.31.1873 E Ie
10010 -45147.3 9.87272 7.45975 £ 9
2 S03 + C = 2 SOz + COz
HKJ DEL HCAlS] lOG10 K K EQ
298.15 -60601.6 44.4482 2.80711.10 E 44
400 -65568.3 35.8459 7.01251 E 35
500 -70599.9 310.8773 7.53654 E 3'"
6100 -75751.9 27.6088 4.106229 E 27
700 -81010. 25.3073 2.02907 E 25
800 -86368.3 23.6086 4.06029 E 23
900 -91824.8 22.3112 2.04724 E 22
110010 -97379.8 21.2948 1.97161 £ 21
- 133 -
-------
TABLE XVIII
THERMODYNAMIC VALUES FOR BARIUM COMPOUNDS
Cp (T)
HO Sf A B C D
f
BaOl ":132.07 16.795 12.733 1. 0392-3 1. 9829+ 5
Ba(}zH}z -226.02 (12.613) 16.90 21. 90 -3
BaC03 -287. 16 26. 781 20.76 1. 1694-2 4. 7708+ 5
BaS03 -282.6 28.60 19.64 1. 614 -2 1. 98 +5
BaS04 -349.99 31. 487 33.759 3.401 -5 8. 394 + 5
BaS -106.0 19.52 (
BaSi03 -359.5
Ba3(P4h -998.0
BaHP04 -465.8
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
~hus,9.16-3 is 9.16 x 10-3. .
,.
.
- 134 -
-------
lCK)
298 e1 5
41010
5100
600
700
8010
9100
110010
TCK)
298. 1 5
400
51010
6010
700
800
900
1101010
TCK)
OVERFLOW
298.15
41010
51010
61313
71310
81010
9010
110121121
TCK)
298. 15
412110
512110
610121
70121
81010
9121121
11211010
T ABLE XIX
REACTIONS OF BARIUM COMPOUNDS
BaC03 + SOz
DEL FCCALS)
-16633.9
-161410.2
-15553.7
-14933.3
-14313.6
-13717.3
-13161.1
-12659.1
---
+- BaS03 + COz
LO G 10 K
12.20101
8.82378
6.810251
5.44264
4.47154
3'-74959
3. 19783
2.76826
_..-..,,,,,,,,-
K EQ
1.58523E+12
666461819
6.34621E+106
2771099.
29616.8
5618.105
1577.
586.491
Ba(OHh + SOZ ;:: BaS03 + HzO
DEL FCCALS)
-43966.2
-4441217..6
-451013.9
-457410.8
-46566;4
. -47480.7
-48479.1
-495Mh2
LOG10 K
32.247
24.2774
19.6871
16.67108
14.5472
12.9 78 7
11 . 7792
10.8377
DEL r- ( CALS)
Ba(OHh + 1/2 Oz + SOZ ~
I N 5810
-1104911.
-103267.
-1102325.
-1101834.
-1101688.
-1101825.
-112122107.
-HJ28107.
BaC03 +
DEL Fe CALS)
-77578.9
-74999.3
-72864.9
-711026.8
-69435.3
-681061.7
-66888.9
-65906.2
- 135 -
LOGIIO K
76.9471
56.4553
44.7525
3701149
31.7671
27.8337
24.8338
22.4817
1/2 Oz + SOZ -:.
LOGIIO K
56.910102
41.101017
31.8679
25.8867
21.6914
18.61045
16.2524
14.4122
K EQ
1.76594E+32
1.89410E+24
4.86526£+19
4.68628£+ 16
3.52542E+14
9.52213£+12
6.01513E+l1
6.88210£+10
BaS04 + HzO
K Ebi
5.789610£+76
2.853310£+56
5.65587E+44
1.310278£+37
5.84864E+31
6.81791£+27
6.82003E+24
3.103176£+22
BaS04 + COz
K £Q
7.947104£+56.
1.1010397£+41
7.37748£+31
7.710333£+25
4.91339£+21
4.102257£+18
1.788102£+ 16
2.56366E+14
-------
TABLE XX
THERMODYNAMIC VALUES FOR CALCIUM COMPOUNDS
CALCIUM
Cp(T)
HO So A B C D
MO' -151,730 9.484 11. 857 1.0798-3 0 166,040
M(OHh -235,600 19.924 25. 131 2.8822-3 0 450,780
MC03 . -288, 110 22. 194 24.965 5.237-3 0 619,700
MS03 -275,880 24.201 18. 770 1.618-2 0 166,000
MS04 -240, 190 25.491 17. 220 2.337-2 0 32,560
MS -115, 300 13.500 10.20 3.80-3 0 0
MSi03 -377,400 20.900 25.85 3.94-3 0 565,000
M3(P04h -435,200 21.0
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus,9.l6-3 is 9.16 ~ 10-3.
- 136 -
-------
HI<)
298. 1 5
4100
5100
600
700
800
900
11300
HI<)
298. 15
400
5100
600
700
800
9010
1000
HK)
298. 15
400
500
6010
700
800
900
11000
HK>
298.15
400
5100
61010
7100
800
900
.1000
TABLE XXI
REACTIONS OF CALCIUM COMPOUNDS
CaC03 + SOz -+ CaS03 + COz
DEL Fe GALS)
-9019.91
-8417.59
-7535.64
-6488.44
-5340.43
-4132.57
-2894.37
-1648.93
LOG10 K
6.61565
4.60185
3.29576
2.3648
1.66833
1 . 12963
.703262
.360585
K EQ
4.12711E+06
39981.1
1975.86
231.633
46.5945
13.4781
5.04966
2.29395
Ca(OH}z + SOz -+ CaS03 + HzO
DEL F
-24174.8
-23114.3
-218510.1
-20442.6
-18935.6
-17358.
-15731.4
-14072.6
LOG10 K
17.731
12.6365
9.55625
7.451058
5.91542
4.74477
3.82233
3.07736
CaSi03 + SOz -+ CaS03 + SiOz
DEL Fe CALS)
-31319.3
. -24685.3
-17517.8
-9792.94
-1555.88
7171.46
16380.8
26072.6
LOG10 K.
22.9711
13.4953
7.6615
3.56917
.486051
-1.9603
-3.98013
-5.7015
K EQ
5.383041::+17
4.329891::+12
3.59960£+09
2.82214£+07
823037.
55561.
6642.54
1194.98
K £Q
.9.35667£+22
3.12844£+13
4.58674£+07
3708.22
3.06232
1.09572£-02
1.04681 E-04
1.98839E-06
CaC03 + 1/2 Oz + SOz -+ CaS04 + COz
DEL F
-66408.8 .
-63368.4
-59930.4
-56212.7
-52303.7
-48258.8
-44117.1
-399108.1
- 137 -
LOG10 K
48.7075
34.6432
26.21109
20.4875
16.3395
1301914
110.7194
8.72'102
K Ebi
5.09925£+48
4.39745£+34
1.62521 £+26
3.07223E+20
2.18535E+16
1.55394£+13
5.24051£+10
533357344
-------
HK)
298. 15
400
500
600
700
800
900
1000
TCK)
298.15
400
500
6121121
7~0
800
900
100121
TCK)
298.15
400.
500
600
70121
800
900
1000
TABLE XXI
(Continued)
.
. Ca(OH}z + 1/2 Oz + SOZ -. CaS04 + HZO
D£L f( CALS) .
-81563.7
-78065.1
-74244.8
-7121166.8
-65898.8
- 6 1 48 4. 3
-56954.1
-52331.7
LOG10 K
59.8229
42 . 6 778
32.4714
25.5732
20.5866
16.8066
1 3 . 8384
11.4438
K £Q
6.65101£+59
4.76236E+42
2.9612180£+32
3.74310E+25 .
3.86016E+20
6.4121583E+16
6.8936121£+13
2.77840E+l1
. CaSi03 + SOZ + 1/2 Oz -. CaS04 + SiOz
DEL f( CAL~)
-88708.2
-79636.1
-69912.5
-59517.2
-48519.1
-36954.8
-24841.9
-12186.6
LOG10 K
65.1063
43.5367
3121.5767
21.6918
15.1572
10.1015
6.03598
2.66494
CaS + 2 SOz -. CaS04 + Sz
DEL f( CALS)
-36624.5
-31052.9
-25761.8
-2121596.7
-15540.~
-10589.8
-5746.93
-1017.25
LOG10 K
26.8622
16.9764
11.2671
7.50673
4.85482
2.8947
1.39636
.22245
- 138 -
K EQ
1.15606E+65
3.44091E+43
3.77275E+30
4.91835£+21
1.43627£+15
1.26329£+10
1.121863Bt+06
462.313
K EQ
7.28121£+26
9.472101£+16
1.84968£+11
32116345
71583.9
784.699
24.9094
1.66897
-------
TABLE XXII
THERMODYNAMIC VALUES FOR COBALT COMPOUNDS
Cp(T)
Co(+ 2) HI sf A B C D
CoOl -57.073 12.655 11. 534 2.0402-3 -3.9896+4
Co(OHh -131.2
CoC03 -173.3 21. 99 17. 17 1. 875 -2 9.9 +4
CoS03 -161.75 25.5 18.44 1. 714 -2 -4.0 +4
CoS04 -207.34 27.067 30.095 9.915 -3 6.915 +2
CoS -22.76 16. 18 10.5952 +2.51 -3
Co(+ 3)
C03)4
Co(OHh
-216.2
-176.6
24.607
30.818
1. 7072-2
5.7575+5
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers .of 10.
Thus,9.l6-3 is 9.16 x 10-3.
- 139 -
-------
HK)
298.1::>
4100
51010
600
700
800
900
1000
'1 C K)
29~ . 1 j
41010
5100
61:'H1
7100
81010
91{)0
110100
TCK)
298. 1 ~
4010
5110
6010
7110
8010
901{)
1101010
TCK)
298 . 15
41010
5/{)0
600
700
800
9100
110100
TABLE XXIII
REACTIONS OF COABLT COMPOUNDS
CoC03 + SOZ
UEL Fe CALS)
-110148.
-9928.4
- 9 7 1 9. 42
-9547.96
-94310.65
-9379.25
-9403.54
-9512.44
-+ COS03 + COz
LOGIIO K
7.443106
5.42781
4.251185
3.47988
2.94611
2.56379
2.28483
2d98016
K t:bi
2.77373£+07
267798.
1 781 7. ':)
3019.14
883.301
366.263
192.677
12((,.271
CoC03 + SOZ + 1/2 Oz -+ CoS04 + COz
iJ£L H CAL~)
-48899.:'
-46766.3
-44912.5
-43276.7
- 4 1 8 42 . 4
-40597.5
-39534.2
-38647.3
L()(j 10 K
35.86::>3
25.::>669
19.6428
15.7728
13.10714
11.0972
9 . 60584
8.4::>132
2 SOz + CoS ~ COS04 + Sz
DEL H (;AL;j)
4014.69
91106.22
13617.8
177::>7.7
21582.5
25124.9
28404.4
31432.5
SOz + 2 CoS
UEL fCCAL;:)
-110148.
-9928.4
-9719.42
-9547.96
-94310.6::>
-9379.2::>
-9403.54
-9512.44
- 140 -
LOG10 K
-20944::> 7
-4.97032
-5.9::>::>85
-6.47202
-6.74231
- 6.86783
-6.9101::>6
-6.8736
-+ 2 CoO + 3/2 Sz
LUG110 K
7.44306
::> . 4278 1
4.2508::>
3.47988
2.94611
2.56379
2.28483 .
2.08016
K Ebi
7.33368E+35
3.68914£+25
4.393109£+19
5.92635E+15
1 . 1 7878 £+ 13
1.2511.i911i:+ll
4.103497EH.J9
2. 82697t!..+08
K i::bI
Io13614E-ll.i3
1.165118E-105
1.10702£-06
3.37273£-107
1.81004E-07
1.3S:.J73i::-LH
1.254401:.-107
1.;;S;;S78H':-107
K EQ
2.77373£+07
267798.
1 78 1 7. :.J
3019014
883.301
366.263
1 92 . 677
120.271
-------
TABLE XXIV
THERMODYNAMIC VALUES OF COPPER COMPOUNDS
Cp(T)
Cu(+2) Hf So A B C D
£
CuO -39.49 10. 187 9.267 - 4.797-3
Cu(OH}z -107,-' 2
CuC03 -142. 10 21. 023 14.91 2.151-2 1. 39+ 5
CUS03 -127.28 25.70 16. 18 1. 99 -2
CUS04 -184.22 27.067 18.805 1. 718-2 2. 792+ 3
CuS -11. 6 15. 9 10.60 2.64-3
Cu(+ 1)
.
CuzO -40.78 22.521 14.893 5.698-3
CUZC03 -142.29 37.63 20.53 2.241-2 1. 39 + 5
CUZS03 -127.06 40.60 21. 8 2.08 -2
CUZS04 -179.51 38.463 24. 19 23.40 -2 5.8 +4
CuzS (103) -19.931 28.883 19.492
CUzS (350) 23.24
20.31
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus,9.16-3 is 9.16 x 10-3.
- 141 -
-------
HK)
298.15
400
51010
6100
7160
8010
9010
110010
1'00
298. 15
4~j0
::>016
6(0)
7I:Jij
81~0
900
1000
HK)
298 . 1 5
4100
50\0
600
71010
8010
9010
10160
TABLE XXV'
REACTIONS OF COPPER COMPOUNDS
CuC03 + S02
DEL F(CALS)
-722~.97
-7125.2
-71032.92
-6978.16
-6977.55
-7042.85
-7183.84
-74109.44
CuS + 2 S02 ~
DEL HCALS)
l::>h':lI.2
21Hjj.2
26121.';:1
31f:141.7
3 ::><5 62 . -,
40::'8~:;. 1
45187.4
49677.1
~" CUS03 + CO2
LOG10 K
5.29988
3.89531
3.07589
2.54328
2.17977
1.92514
1.7455
1 . 62028
CUS04 + S2
LUL,10 K
-11.6::>::)4
-11.::'301
- 1 1 .4246
-11.3186
-11.2kiJ4
-11.k192:>
-10097Y4
- HJOb 633
CuC03 + S02 + 1/2 O2 ~
DEL I- (CALS)
-57267.8
-54987.
-::>2144.6
-50532.2
-48366.3
-46258.3
- 442 1 7. 1
-422::>0.8
- 142 -
LOG10 K
"42.10031
310.0611
23.10682
18.4171
1 5. 1095
12.6446
Hi . 743 7
9.23932
K EC:J
199472.
7858.01
11910.94
349.369
151.275
84.1675
55.6:>4
41.714
f< EU
2.21 l!tib r.: - 1 2
2.H':i66.1.jE-12
3.7621651::-12
4.3::;7911::-12
6.26G46t:-12
8.08239':':-12
1.~4851£-11
1.369991::-11
CUS04 + CO2
K EbI
1.01071061:.:+42
1.151!06£+31U
1.170010£+23
2.61293£+18
1.28676£+ 1:>
4.41150i+12
5.54215E+Hi
1.73;,10i::+H9
-------
TABLE XXV'
(Continued)
2CuS+ SOZ ~ 2CuO+ 3/2Sz
HK)
298.15
400
Ski lD
600
700
81<10
900
11000
LJEL F< CALS)
HJ0662.
11004110.
100326.
1003610.
100478.
100656.
100877.
101122.
TC K)
298 . 1 :>
400
500
600
71210
81010
9010
'1000
CUZC03 + SOz
DEL Fe CAL::»
-6307.02
-6032.4
-5769.42
-5543.96
-5372.65
-5267.2~
-5237.54
-5292.44
LO G 10 K
-73.8306
-54.8936
-43.8704
-36.5774
-31.3889
-27.5142
-24.:> 1\,:)5
-2201131
~ CUZS03 + COz
LOG10 K
4.62588
3.29788
2.52329
2.021057
1 .6784
1 .43979
1.27259
1.15734
K EQ
1.47720£-74
1.27765£-55
1.32327£-44
2.64633£-37
4.108426£-32
3.06083£-28
3.0865!{j£-25
7.70770£-23
K EQ
42255.6
1985.57
333.65
104.851
47. 6871 .
27.5289
18.7324
1 4 . 3662
CUZC03 + SOZ + 1/2 0z -:. CUZS04 + COz
T(K)
298 . 1 5
400
500
6100
7100
800
900
10100
DEL !'"(CALS)
-510814.2
-4139S.
-32156.7
-22952.7
-13796.6
-4698.33
4333.87
13292.3
- 143 -
LOGI121 K
37.2696
22.63104
14.0639
8.36542
4.3110103
1.28428
-1.053102
-2.90673 .
K EbI
1.86047E+37
4.26997E+22
1.15854E+14
2.31961£+08
20418.8
19.2432
8.8 ::;068£-02
1.239571::-103
-------
T395
-17.8659
-18.84::>1
-19.59102
-210.1687
K EbI
1.08745£-/()7
1.484231::-12
2.17320E-l::>
2.88704E-17
1.36189E-IS
1.428SIO£-19
2.56943£-20
6.78139£-21
2 CUzS + SOZ ~ 2 CuzO + 3/2 Sz
DEL F < C/-\LS)
80276.3
81791.1
837~3. 1
861076.4
88688.3
91~3::i.3
94576.
97776.9
2 CuC03 +
DEL F< GALS)
-24171.2
-22417.3
-210670.8
-18957.9
-173108.7
-1:'743.4
- 1 4278 . 1
-12927.
- 144 -
LOG10 K
- 58 .8 786
-44.7148
-36.6299
-31.3717
-27.706
-25.02109
-22.9796
-21.3817
SOz ~ CUZS04 +
LOG1l1 K
17.7283
12.2::>54
9.1040:>
6.910':147
S.40719
4.30341
3.46922
:2.82685
K EGI
1.32241£-~9
1.92847£-45
2.34474£-37
4.24911[-32
1.96803E-28
9.52938£-26
1.04798£-23
4.1 S278i-22
2 COz
K EQ
5.349721::+17
1.800561::+12
1.0977::>£+09
8.11846E+106
2::>;)381.
2(1)1 VJ9. ':I
2945.93
671d96
-------
TABLE XXVI
THERMODYNAMIC VALUES FOR IRON COMPOUNDS
Cp(T)
Fe(+ 2) HO Sf A B C D
f
FeO ..:63.762 14. 191 11. 656 7.9993-3 7.597+4
Fe (OHh -135.70 18. 873
FeC03 -178.55 22. 194 11. 625 2.678 -2
FeS03 -165.54 25.3 18.57 17. 1 -2 7.6 +4
FeS04 -220.41 25.682 20.96 1. 974 -2 1. 34 + 5
FeS (138) -22.8 15.200 12.2 2.38 -3 (AH= 1. 195)
II II (AH=5.686)
FezSi04 -343.54 35. 38 36.51 9.36 -3 -6.70 +5
FeSz -42.45 12.70 18.0 1. 182 -3 3. 12 + 5
Fe(+ 3)
FeZ03 -196.42 20.88 23.48 1. 859 -2 3.548+ 5
Fez(COzh -502.66 44.8 40.40 6.872 -2 7.72 + 5
FeZ(S03h -457.4 53.8 44.21 6. 389 .-2 3. 55 + 5
FeZ(S04h -615.6 61. 90 51. 38 7. 181 -2 5. 290+ 5
Fe(OHh -197.0
Note: Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 145 -
-------
l'(K)
298.15
4012.1
5100
610'1
700
800
90~
1000
HK)
298 .'1 S
4010
500
6100
70121
812.110
900
101!10
HK)
298.1~
412.10
51010
600
701!1
80121
900
1010(0
TABLE XXVII
REACTIONS OF IRON COMPOUNDS
FeC03 + SOz
DEL F(CALS)
-8567.57
-3783.91
688.45
4973.19
9088.28
13043.3
16843.
2048B.9
= FeS03 + COz
J-OGI0 K
6.28388
2.106865
-.310112.198
-1.81254
-2.83915
-3.56536
-4.109244
-4.481047
K £bI
1.92257£+06
117.124
.499922
1 .53977£-102
1 . 4 48 2 71:: - ~ 3
2.720471::-(04
8.08283£-05
3.30771£-105
1/2 FezSi04 + SOZ ~ FeS03 + 1/2 SiOz
DEL r(GAL::»
-17653.3
- 6 69 7 . 54
41:;)6.74
15167.
263~4.
37727.4
49293.6
6112.158.4
LOG10 K
12.9478
3.661~1
- 1 .81 798
- ~. ~2 782
-8.23291
-110.3127
-11.9771
-13.3:;)21
K£bI
8.86715E+12
458 6. 84
1.52(063£-102
2.966109£-06
5.84912E-09
4.86758E-l1
1 . 0S4~4E-12
,4.445108E-14
FeC03 + 1/2 Oz + SOz ~ FeS04 + COz
DEL r(l,;ALS)
-~6245.7
-~3641.5
-51312. 1
-4916701
-47185.::>
-4535::>.9
-43,672.
- 42 1 3 1 .
- 146 -
LOG10 K
41.2::>34
29.325::>
22.4416
17.9196
14.7406
12.3979
11;.6112
9.21313
K C:""
1 . 79233t:+ 41
2.1161081::+29
2.76467£+22
8.31101041::+17
5.516333E+14
2.49986£+12
4.08529£+10
1.63354£+09
-------
HK}
298.15
4016
5100
61010
7160
81010
9100
101010
HK)
298'} ~
4010
:> 10 10
6~H1
71010
81010
900
H.i1:'J0
T(K)
298.} =>
41010
5100
6010
7100
800
900
110100
TABLE XXVII (Continued)
1/2 FezSi04 + 1/2 Oz + SOZ
OEL F«(,;ALS)
-65331.4
-56555.1
- 4 7 8 43 . 8
-38973.3
-29919.8
-210671.8
-1 1221 . 4
-1561.S7
LOGIIO K
47.9173
30.9184
20.9248
i4.21043
9.34687
5.65058
2.72652
.341482
~ FeS04 + 1/2 SiOz
K Ebi
8.26647E+47
8.287103E+30
8.410941E+21O
1.6fOI:'J78E:+14
2.22263E:+09
'147285.
532.741
2ol9::>24
FeS + .2 SOz ~. FeS04 + Sz
UEL H GAL::i }
-8894.56
-3421.83
179(1).34
68 72 . S 1
11834.1
16676.4
21396.4
259H8.9
LiJGIIO K
6. ::>2371
1.5707
-.7031016
-~.::>047~
-3.69694
-4.5:;,844
-::>.1988
-::>.68321
K EQ
3.3397SEHJ6
74.2499
. 16461
3.12769£-103
2. vJ093:>t::-04
2.76411"::-05
6.32711!Ji:.:-06
2.1U7393E-06
2 FeS + SOZ ~ 2 FeO + 3/2 Sz
OiL F(GALS)
29185.8
272::>:3.4
25191.6
231iHiJ2.8
207102.8
18299.1
15794.9
13190.::>
- 147 -
LOG10 K
-21.4063
-14.8993
-11.16177
-8.38367
-6.46749
-5.1002162
-3.83776
-2.88448
K i::Q
3.923411:.:-22
1.261101£-15
9.600431:::-12
4.13360E-09
3.408106E-107
9.95362£-106
1.452910£-104
1.316474E-103
-------
lCK)
298 ol S
4/(H1
~01O
600
700
800
9010
10100
HK)
:298 . 1 :)
400
5"'10
6100
700
81010
900
1000
TCK).
298.15
4010
5010
61010
71010
8010
9100
h)0fO
TABLE XXVII (Continued)
1/3 Fez(C03h + SOz
DEL rc GAL~)
-6460.72 .
-6189.11
-::>929.108
-~706.57
-S538.21
-5435.76
-54109.
-S466.~5
~ 1/3 Fe z(S03h + COz
LOG10 K K E~
4.73861 ~4778.9
3.3B355 2418.54
2.59312 391.848
2.107984 1210.181
1.73012 53.7183
1.48585 30.61091
1.31425 20.6184
1.19548 15.6849
1/3 Fez(C03 + 1/2 Oz + SOz ~
UEL F< GAL~)
-52688.
-::>01::>8.4
- 4 7 68 4. 6
-4~:245.1
-42853.5
-410519.6
-382~1.9
-361057.9
LOGlftJ K
38.644
27.4214
20.8551
16.4902
13.31:$73
11.07~9
9.29428
7.885108
1/3 FeZ(S04h + COz
K t::bI
4.405361::+38
2.638511i:+27
7.16378E+21O
3.09154E+16
2.439S4E+13
1.191109£+11
1.96914£+09
7.67499E+107
Fe~(C03h + 2 SOz ~ FeS03 + FeS04 + 3 COz
UEL F7723£+109
- 148 -
-------
HK)
298. 1 :>
400
500
600
7(::)0
800
900
H)(i)(i)
l(K)
298. 15
400
500
600
7160
800
900
10100
HK)
298 . 1 ::>
4100
500
600
700
8010
900
10100
l64.6
-103267.
-HJ7190.
LOG10 K
61 . 1 64
47.2938
3901758
33.8018
30.(i)10~
27.2157
2::>.16912
23.44
K t:bI
1.45895E+61
1.96701E+47
1.49885E+39
6.33523E+33
1.023901::+30
1.64332£+27
1.23377£+25
2. 75436E+23
Fe2(S04h + S02 + 2 FeO Z 4 FeSO If
DEL F(CALS>
-53600.4
-49563.9
-45633.9
-417510.7
-37920.1
-34146.4
-30432.8
-26782.7
LOG10 K
39.3132
27.'1963
19.95153
15.2166
11.8461
9.33383
7.39442
5.8::>678
K 1::GI
2.05670E+39
1.248271::+27
9.083821::+19
1.646571::+15
7.fOI688E+ll
2.156891::+'19
2.47983E+1(J7
719086.
FeS2 + 2 502 ~ 1. 5 S2 + FeS04
U£L F ( CAL':) >
17304.
19.:>61.
21772.2
23943.2
261053.3
28087.
30031.3
31874.
LOG10 K
-12.6916
-10.6939
-9.::>2219
-8.7264
-8.13896
-7.677::>2
-7.29688
-6.97014
K I::bI
2.03424E-13
2. .0.2361 E - 1 1
3.004761::-10
1.81757£-09
7.26169£-09
2.10125£-108
5.0481611::-08
1.07118E-07
2 FeS2 + S02 .~ . 2 FeO + 2. 5 S2
UEL HCALS)
81582.9
73218.9
65155.3
57144.1
49141 . 1
41120.5
33064.8
249610.6
LOG10 K
-59.837
- 4~)' 1028 4
-28.4961
-20.8269
-15.351:)
- 11 .2402
-8.103393
-5.45834
- 149 -
K I::bI
1.455591::- 61/1
9.366541::-41
3.191111::-29
1 . 489 61 t:: - 2 1
4.451141::-16
5.7S207E-12
9 . 24841 I:: - 12) 9
3.48062t:-06
-------
TABLE XXVIII
THERMODYNAMIC VALUES FOR LITHIUM COMPOUNDS
Cp(T)
Hl Sf A B C D
LizO -142.5 9.0519 14.932 6.0776';'3 3. 378+ 5
LiOHz -116.535 10.227 11. 98 8.237 -3 2.267+ 5
LizC03 -290.26 21. 582 20.57 2.279 -2 4. 77 + 5
LiS03 -279.4 26.00 21. 84 2.118 -2 3. 38 + 5
LiS04 -342.58 35.357 24.23 2.382 -2 3.96 + 5
LiSi03 -376.5 20.00
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of'10.
Thus, 9.16-3 i~ 9.16 x 10-3.
- 150 -
-------
i
HK)
296.15
41010
5100
61010
700
6100
91010
10010
TCK)
296.15
400
500
61010
700
8010
91010
1101010
TCK)
296.15
400
51010
61010
71010
61010
9010
1101010
TCK)
296.15
41010
51010
6100
700
6'010
9010
1101010
TABLE XXIX
REACTIONS OF LITffiUM COMPOUNDS
LizC03 +
UEL FC CALS).
-111106.7
-110981.6
- 1 10863. 4
-110762.8
-HJ756.3
-110795.6
-1109110.7
-1111Ii).4
-+
SOz .-
LOG11i:1 K
8.1477
6.010359
4.75118
3.92992
3.361022
2.951096
2.651104
2.42961
LizS03 + COz
K I::bi
1.40509E+08
1.00829E+1i:I6
56367.4
85109.85
2292.04
693.229
447.151
266.911
.....
2 LiOH + SOz .-
DEL FCCALS)
-3121603.2
-29654.1
-29062.6
-28240.8
-274106.6
-2657.2.8
-25749.7
-24946.5
LOG10 K
22.4459
16.3214
12.71107
110.2927
6.56175
7.26361
6.25656
5.45524
LizS03 + HzO
K EQ
2.7919IOE+22
2.09619E+16
5.1367Ii:1E+12
1.96217£+10
364546265
1.83486E+07
1.8105331::+1216
285262.
+ SOz + 1/2 Oz ~
LOG11i:1 K
5101748
37.2112
29.0402
23.61054
19.7384
16.8539
14.6264
1 2 . 6 610 6
LizC03
- U£L F< CALS )
-69772.8
-661065.8
-66399.5
-64767.6
"63183.6
-61657.3
-610197.2
-586110.8.
2 LiOH + SOz + 1/20z
UEL FCCALS)
-89267.3
-86936.9
-64598.6
. -62225.6
-79633.9
-77434.5
-751036.2
-72646.8
- 151 -
LOG10 K
.65.473
47.5291
36.9997
29 . 9 682
.24.9399
21.1665
16.232
15.6663
LizS04 + COz
K EQ
1.495691::+51
1.626331::+37
1.1097103E+29
4.031093£+23
5.47474E+19
7.14282£+16
4.23093E+14
7.2546IOE+12
..... .
.- LIZS04 + COz
K EQ
2.97192E+65
3.381107E+47
9.99356t::+36
9.29439E+29
8.71i:175Ii:1E+24
1.46729£+21
1.710569£+18
7.69593E+15
-------
TABLE XXX
THERMODYNAMIC VALUES FOR MAGNESIUM COMPOUNDS
Cp(T)
Hfo So A B C D
f
MgO -143.63 6.4025 10.175 1. 7392-3 1. 4788+ 5
Mg(OH)z -220.82 15.077 13.034 1. 579 -3
MgC03 -263.98 15.696 18.613 1. 3794-2 4. 1592+ 5
MgS03 ::'241. 0 22.5 17. 09 1. 684 -2 1. 48 +5
MgS04 -305.5 21. 9 16. 53 2. 18 -2 1. 578 + 3
MgS -83.0 10.6 9.24 2. 5 -3 7.93 +2
MgSi03 -357.63 16. 197 24.535 5.437 -3 5.867 + 5
Mg3(P04h -960.617
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 152 -
-------
T1010
610 II:)
71!J0
81210
912110
1000
HK)
298.15
4100 ..
5121121
61210
70121
810121
9100.
10121121
TABLE XXX!
REACTIONS OF MAGNESIUM COMPOUNDS
MgC03 + SOZ .
DEL F 68 .. 1
-1228.13
-984.035
LUG10 K
3.6766':5
2.1912161
1 . 41213~2
.929333
.626891
.428639
.29841216
.215187
MgSi03 + SOZ -- MgS03 + SiOz
DEL F
-------
HK)
298.15
41010
5010
61010
7010
8010
9010
1000
TCK)
298.15
400
5100
61010
71010
8100
900
1000
HK)
298. 1 5
41010
51010
600
71010
600
91010
10010
TCK)
298. 15
4010
51010
61010
7100
81010
91010
1101010
TABLE XXXI
(Continued)
Mg(OH}z + SOZ + 1/2 Oz
DEL F(CALS)
-621028.2
- 5848 6. 2
-551056.7
-jI669.3
-48322.8
-451018.2
-41757.7
-38:'43.6
MgSi03 +
DEL Fe CALS)
-74119.7
-65308.9
-55839.8
-457102.9
-34968.7
-23674.
.-11836.5
537.927
MgS
. 2 SOz ~
D£L F(CALS)
-34028. :)
-28426.
-2311010.9
-179101.6
-12813.2
-7831 .98
-29610.71
1795.21
LOG11ii K
45.4946
31.9741
24.10794
18.8315
15.10959
12.3056
10.1461
8.42864
-. MgS04 + HzO
K Ebi
3.12296£+4:'
9.421211::+31
1.2101056E+24
6.78498E+18
1.247lii9E+15
2.02127£+12
1.39988£+110
268311654
SOz + 1/2 Oz -. MgS04 + SiOz
LOGlIcJ K .
j 4 . 3 63 1
3S.704
24.4219
16.657
10.9241
6.47123
2.67::>99
-.117633
Sz
LOG10 K
24.9582
1 ::> . :I 410 4
110.11033
6.52454
4.0026
2.141085
.719381
-.392573
2 MgS + SOz ~ MgO +
DEL F(CALS) LOG10 K
-8248.87 6.1051013
-9477.11 5.181109
-11116.7 4.86194
-131038.3 4.75197
-15175. 4.741063
-17491.9 4.78137
-19969.2 4.852102
-22595.3 .4.9411
- 154 -
MgS04
3/2 Sz
K t::bI
2.3lii719E+54
5.105862£+35
2.64172E+24
4.53959£+16
8 . 39678 E + 1 Iii
2.95958E+lii6
751.6101
.762724
K Ebi
9.108139£+24
3.471032£+15
1.268591::+110
3.34608£+06
11211064.6
138.309
5.2406
.4104974
K EQ
1.12235E+lii6
151736.
72768.4
56489.3
551033.9
610446.2
71124.7
87317.8
-------
TABLE XXXII
THERMODYNAMIC VALUES OF MANGANESE COMPOUNDS
Cp(T)
HO So A B C D
f £
MnO -91. 93 14.265 11. 104 1. 94 -3 8. 79 + 4
Mn(OH}z -165.677 21. 095
MnC03 -213. 74 20.474 2 1. 99 9. 3 -3 4. 69 + 5
MnS03 -197.37 24.40 18. 01 1. 704-2 8.8 +4
MnS04 -253.95 26.781 29.241 8.916-3 7. 038+ 5
MnS -49.452 18. 682 11. 396 1. 799-3
MnSi03 -302.21 21.2836 26. 398 38.77 -3 6. 156+ 5
Mn203 -229. 11 26.398 24.726 8.376-3 3. 228+ :;
Mn(OHh -212.0
MnzCQ) -545.46 44.6 41. 65 5.851-2 7.4 +5
Mn2(S03h -502.39 53.6 45.46 5.368-2 3. 23 + 5
Mn2(S04h -666.9 61.7 52.63 6. 16 -2 4. 97 + 5
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 155 -
-------
°1 (K)
298.1~
4 ~)\o
::>~0
6kJ0
700
8160
91010
1101<)10
HtO
~9i3 . 15
4160
5010
MilO
'Ii() k'J
8100
9016
11600
1(K)
~98 01 ::>
400
::>V)Vi
60(tj
70~
8160
9180
110100
HK)
298.15
400
5010
6!!J0
700
800
900
100f(J
TABLB XXXIII
REAC TIONS OF MANGANESE COMPOUNDS
MnC03 + SOz ~ MnS03 + COz
DEL F(GAL~)
-::>452.06
-SllS.S6
-4575.63
-3927.109
-3221.7
-2492.51
-1763.6
-11054.12
MnSi03 + SOz ~
IJI::L Fe GAL::»
-27944.3
-22412.3
-16249.9
-9482.34
-216i3.44
5662014
13996.2
~~830.9
LOG10 K
3.99881
~.7'J665
2.01011b
1.43128
1.00645
.681322
.428::>12
.:230513
K t::l:J
9972.58
626.114
100.272
26.9949
1001496
4.80089
2.682;;$3
1.701!12S
MnS03 + SiOz
LO G 110 K
21!1.4957
12 . 2 5~ 7
7. H:i698
3.4~596
.677414
-1.54773
-3.4121074
-4.99261
K EbI
3.13113ii.:+20
1.78935E+12
1.279311::+07
28:>7.35
4.7::>789
2.83314£-02
3.97433£-04
1.01717£-fOS
ut. L F ( GI.I_,:) )
MnSi03 + 1/20z + SOz -:. MnS04 + SiOz
-77') Gis. 4
-7i!ib9::>.3
-62vJ91.4
-::>37::>0.1
-4SfiS7.4
-35999.8
-26562.
-167G6.o
LU G H) K
::>701::>66
38.320ts
27'} ::,6
19.5899
14.0758
9.b404S
6.4j393
3. 6j 770
i< c:u
°1. 4341~)i3t::+:,7
2.092991::+38
1.432201:.:+27
3.S8988E+19
1 01 9069ii:+ 14
6.92548 iHj9
2.84397£+06
L:, 5 L:, 7 . 62
-+
MnC03 + 1/2 Oz + SOz - MnS04 + COz
Dii.:L F
-------
HK)
298. 1 ::>
400
t>00
600
700
800
900
1000
HK)
298. 1 S
4010
:>00
600
7!U0
cs016
90v;
1000
°1'CiO
f:::98.1::»
LI/(j(:.'
5100
61::10
70f./!
816'"
9016
100~
OJ (K)
298. 1 t>
4~1{tj
::>1010
61016
700
8010
900
1000
TABLE XXXIII (Continued)
MnS + 2 SOz :;:
uEL F4E-!6S
6.81018E-104
1/3 Mnz(G03h + SOZ ~. 1/3 MnZ(S03h + GOz
iJl::L ~. < Gi-;L.::; )
-71Siki.65
-6919.1~;j
-66::>';1.101
-6436.5
-6:268.14
-6165.69
-6138.92
-6196.78
L0GH.l K
::».27::S98
3.7b26
2.91236
r.:.34::)ij7
1.95blS
1 . 68537
1.49161
1.35::>1
K El>:
187922.
6~J61. 79
81-(.2:>1
221.752
9t::..8133
48. 4 5 9
31.1!J176
22.6:)16
1/3 Mnz(G03) + 1/20z + SOZ ~ 1/3 MnZ(S04h + GOz
iJEL f
-5(1517.6
-4oknS.l
-45686.5
-43352.7
- 41 ~8 4.9
-38891.
LOG10 K
40. 721 9
28.9702
22.0942
17.5227
14.2723
11.8504
9.98264
8.:'046
- 157 -
K El:J
5.27085i::+40
9.336271:::+2~
1.24221 E+22
3.;)3210E+17
1.872161::+14
7.08517E:+l1
9.608111:::+09
319::>97S..,Q
-------
HK)
298 . 1 ~
4110
::;00
6.010
(1£110
800
9010
10100
HK)
o \tt:R FLO \~
298. 1 5
40ft)
51010
6010
7011
800
90(tJ
1000
HK)
298. 1 j
400
51010
60£1
700
800
900
1000
TABLE XXXIII (Continued)
-+
Mnz(C03b + 2S0z +-
Di::L F050.4
-81243.5
-877:53.6
-94:>80.6
-1101729.
MnS03 + MnS04 + 3 COz
LOG10 K
42 .83::> 7
34.7982
30.2568
27.3531
25.3802
23.9872
22.9808
22.2458
K El:J
6.85039£+42
6.28287~+34
1.816618£+30
2.254941i.:+27
2.40014E+25
9.71020i::+23
9.56687E+22
1.76130£+22
Mnz(C03b + 2 SOz + 1/2 Oz ~ 2MnS04 + 3 COz
DEL F.
-11::>1023.
- 1 1 9 3 18 .
-124132.
-129416.
-135139.
-141286.
79.4966
6ft1. 8 662
50.3058
43 . 48 7 1
38 . 7786
35.3754
32.8354
31!i.8962
MnZ{S04b + 2MnO + SOz ~
DEL !'.78960£+76
7.34906£+60
2.102215E+50
3.06978 E+ 43
6.1/)(21648 £+38
2.37362E+35
.6.84592£+32
7.87454£+310
4 MnS04
K EQ
. 5.49374E+59
1.35732£+42
3.51459£+32
3.56969£+26
3.37898 E+22
4.9301!J3£+19
4.2kJ936E+l"
1.195104£+16
-------
TABLE XXX;tv
THERMODYNAMIC VALUES OF MOLYBDENUM COMPOUNDS
Cp(T)
Mo(+ 4) HI Sr A B C D
MoOz -140.83 11. 0562
MoSz -55.97 15.098
Mo(+ 6)
Mo03 -177.885 18.572 20.06 5.898-3 .3. 679+ 5
MoS3 '-61. 4689 15.887
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3. '.
- 159 -
-------
TABLE XXXV
THERMODYNAMIC VALUES OF NICKEL:_COMPOUNDS
Cp(T)
Ni(+ z) Hi 51 A B C D
NiO (250) -57.264 9.078 4.988 3.7555-2 3.8893+ 5
(25 -250) 11. 1 76 2.0187-3
Ni(OH}z -128.6 19.0
NiS03 -155.86 25.4 27.69 7.28 -3 -5.8 +4
NiS04 -218.5 18.586 30.078 9.917 -3
NiS -17.48 16. 10 9.245 12.795 -3
Ni(+3)
N iZS3
Ni( OHh
-43.36
-162. 1
36.58
Note:
Positive and negative integers after values in
Columns B an D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3~
- 160 -
-------
lCK>
298. 1 5
4100
5100
600
700
800
9Ij,~
10010
TCK>
298.15
40kJ
5016
. 60~)
780
81010
960 .
1000
TABLE XXXVI
REACTIONS OF NICKEL COMPOUNDS
NiS + 2 SOz
DEL FCCALS>
-9920.56
-4551.94
294.943
479 1 . 06
8977.22
12878.9
16S1~2.4
19887.7
2 NiS + SOZ
.DEL F(CALS)
3::>127.4
33216.6
311101.
28784.1
26287.5
23625.4
2108106.6
17836.9
- 161 -
-+ Sz + NiS04
LOG10 K
7.27623
2.48B52
. -. 128995
-1.74616
:-2.~0446
-3. 521£:j43
-4.01211
-4.34901
K t.:bi
1.88898E+07
307.979
.7431027
1 .79405[-02
1.56871[-03
3.01699£-104
9.72494[-05
4.47701[-105
-+
2 NiO + 3/2 Sz
LO G 10 K
-25.7642
-1801593
-13.61022
-110.49107
-8.21214
-6.45794
-5.05551
-3.90105j
K Ebi
1.721221::-26
6.92909£-19
2.499108E-14
3.23049[-11
6.13j61O[-09
3.483871::-167
8.B0022£-06
1.25734£:;-04
-------
TABLE XXXVII
THERMODYNAMIC VALUES FOR POTASSIUM COMPOUNDS
Hi sf A B C D
KzO -86.362 23.484 17.91 9.32 -3 4.0 +4
KOH -101. 69
KZC03 -271.87 36.074 23.550 2.603 -2 1. 79+ 5
KZS03 -266.9 37.40 24.82 2.442 -2 4. 0 + 4
KZS04 -342.34 41. 975 28.76 2.379 -2 4. 257+ 5
5950 C (~H=2. 25) 33.59 1. 3395 -2
KzS -87.867
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 162 -
-------
TCK>
298.15
400
500
600
1010
800
900
1000
TCK)
298. 1 S
400
500
600
7k:10
800
900
1000
TABLE XXXVIII
REAC TIONS OF POTASSIUM COMPOUNDS
K2C03 + 502 -+
DEL FCCALS)
-16076.9
-15634.8
-15207.4
-14817.6
-1 4481 .9
-14212.
-14017.9
-13908.4
K2503 + CO2
LOG10 K
11 . 791 6
8.54747
6.65106
5.40046
4.52409
3.88483
3.40602
3.04147
KZC03 + 50z + 1/20z -+
IJEL FCCALS>
-85575.2
-82503.6
-78986.9
-75069.2
-70823.1
-66305.5
-61562~
-566310.5
LOG10 K
62.7651
45.1043
34.5454
27.36
22..1249
18.1244
1 4 . 9 58 1
12.3838
- 163 -
K EQ
6.188271::+11
3.52751£+08
4.41772E+06
251454.
33426.4
7670.56
2546.92
1100.2
KZS04 + COz
K EQ
5.82211£+62
1.27150E+45
. 3.51078E+34
2.29070£+27
1.33334£+22
1.33181£+18
9 .07949 E+ 1 4
2.42012£+12
-------
TABLE XXXIX
THERMODYNAMIC VALUES FOR SODIUM COMPOUNDS
Cp(T)
HI sf A B C D
NazO 102.87 16.986 15.693 5.3968~3
NaOH -101. 91 27.71 -7.0231 5.5498-2 -2.036-5 5.8106+ 5
NaZC03 -269.72 32.49 16.874 3.2395-2
NaZS03 -260.40 34.879 22.60 2.05 -2
NaZS04 -330.64 35.692 15.533 5.2773-2
NazS -92.96 22.48 19. 81 1. 64 -3
NazSi03 . -362. 65 27. 19 31. 39 9.597 -3 6.467+ 5
N a3P04:' -288. 35
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 164 -
-------
HK)
298. 15
40~
500
600
700
80~
900
101210
HK)
298. 1 ~
4100
~00
600
700
8100
900
10/010
TCK)
298015
400
500
600
71010
81010
91010
11211010
HK>
298.15
412110
500
6010
700
800
900
.101010
TABLE XL
REACTIONS OF SODIUM COMPOUNDS
NaZC03 + SOz
-+
+-
NaZS03 + COz
DEL F< CALS)
-121043.8
-11973.6
-12072.1
-12321.1
-12712.1
-13241.2
-139107.3
-14711.5
2 NaOH + SOz
DEL FeCALS)
-3307:::>.4
-34133.4
-3~91~.2
-38477 .
-41~21O.2
-4S942.2
. -5f084:>.
-56~36.7
LOG10 K
8.83352
6.54589
5.27982
4.49106
3.97123
3.61944
3.37913
3. 21 707
K E:Q
681583092
3.51468E+06
1910468.
3121945.7
9359.01
4163.31
2394.01
1 648 . 44
-+ NaZS03 + HzO
LOlill!J K
24.2~';11
1 8 . 6606
15.71077
14.023~
13.10645
12.SS82
12.3~41
12.3633
NaZC03 + 1/2 Oz + SOz
DEL FeCALS) LOG10 K
-75220.5 55.1704
.-71701~4 39.1988
-68155.6 29.8083
-64557. 23.5287
-60930.2 19.10344
-57294..4 15.6613
-53665.2 13.10393
-50056.4 10.9462
K EGI
1.81596E:+24
4.57696J::+l~
~.1016fdE+l~
1.10:>551.1£+14
101612115E+13
3.6lS61~+12
2.~~992b.:+12
2.3108461::+12
-+
+-
NaZS04 + COz
K EQ
.1.48056£+55
1.58041 E+39
6.4307IOE+29
3.37793£+23
1.08252E+19
4.5844IOE+15
1.109480£+ 13
8.83539£+10
NazSi03 + SOz -+ NaZS03 + SiOz
DEL F(CALS)
-31897.6
-25935.8
-19300.7
-12032.7
-4200014
4161.92
13037.2
224210.9
LOGIIO K
23.3953
14. 1 79
8.4413
4.38547
1.31211
-1.13765
-3.16773
-4.90296
- 165 -
K EQ
2.48463£+23
1.509'97£+ 14
2. 76247E+108
24292.1
210.5169
7.28366E-02
6. 79630E-104
1.251037E-12I5
-------
I .
,
'}CK)
29801:'
4010
51010
600
7010
81210
912110
10100
TCK)
298.15
400
500
6/{)0
70/{)
800
900
1/{)IOIO
TCK)
298. 15
400
500
600
700
8100
900
1000
TCK)
298. 15
4010
500
60121
7100
800
9100
1101010
TABLE XL
(Continued)
2 NaOH + SOz +
1/2 Oz
IJt:L Fe CALS)
-962:;2.
- 9 38 6 1 . 2
-91998.6
-90712.9
-9101038.3
-89995.4
-90603.
-91881.6
LOl;;10 K
7121.596
51.3135
410.2361
33.061:;
28 . 1 277
24.6
22.IH43
20.092:::>
NazSi03 + SOz + 1/2 Oz ~
. UEL Fe CALS)
-95074.3
-85663.6
-75384.2
-64268.5
-52418.3
-39891.3
-267210.7
-12924.
NazS + 2 SOz
DEL FCCALS)
-49802.4
-43255.3
-:-367106.9
-301051~4
-23312.7
-16515.6
-9683.43
-2837.77
LOG10 K
69.7322
46.8319
32 . 9697
23.4235
16.3753
110.91042
6.49248
2.82619
-0- NaZS04 + Sz
LOGie K
36.5275
23.6474
16.054
1 0 . 9526
7.28283
4.5145
2.35284
.6210557
~ NaSO" + HzO
K t:<>I
3.94468E+70
2.1058~7t:+:>1
1.722431:.:+40
101 :J2l :>1::+33
1.34189t:+28
3.98131£+24
1.1033481::+22
1.23730£+20
NaZS03 + S,iOz
K EQ
5.39720E+69
6.78971E+46
9.32681E+32
2.65165E+23
2.37310E+16
8.02034£+110
3.10800£+06
670.182
K EQ
3.36917E+36
41.44060£+23
1.13233£+16
8.96683£+10
1.91793£+07
32696.7
225.339
4.174104
2 NazS + SOz ~ 2 NazO +
uEL Fe CALS)
93916.5
93117.8
92257.7
91368.
904610.4
8953:'.
88587.5
87611.8
- 166 -
LOl;;10 K
-68.883
-50.9071
-41O.349:J .
-33.30~3
-28.2596
-24.4742
-.21.5246
-19. 1 588
1. 5 Sz
K El1i
1 .30906E-.69
1.23865£-51
4.47237~-41
5.00839t:;-34
5.50079£-29
3.356109£-25
2.98814t:;-22
6.93791£-20
-------
TABLE XLI
THERMODYNAMIC VALUES FOR TIN COMPOUNDS
Cp(T)
Sn(+ 2) Hfo Sf A B C D
SnO -68.325 13. 555 9.5464 3.4975-3
Sn(OHh -134. 1 37.0
SnS -24.320 18. 395 8.4795 7.428-3 9. 526+ 4
Sn(+ 4)
SnOz -138.75 12.504 17.652 2.3986-3 5. 1579+ 5
SnSz -39.896 20.880 15. 510 4.197 -3 9.63 + 1
Sn( C03}z -330.04 33.9 28.94 3.58 -2 7.94 +5
Sn(S03h -295.36 42.9 3 1. 48 3.26 -2 5. 16 +5
Sn(S04}z -393.40 37. 1 36.26 3.788 -2 6.32 +5
Sn(OH)4 -265.3
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 167 -
-------
L_-
i
!
'I (K)
298.1::>
4~0
::>00
b/()i!J
7016
blO/()
900
110010
HK)
298. 1:> ,
4100
~00
600
700
8100
900
1000
T(K)
298 ol 5
400
5010
600
7010
8010
90I!J
11O/()(1
TABLE XLII
REACTIONS OF TIN COMPOUNDS
2 SnS + SOZ ~ 2 SnO + 3/2 Sz
UEL io(L;ALS)
2::>384.3
23309.1
21141.
HHS37.9
16402.3
.13tS37.3
11144.~
b;j~S.90
LUbllo K
-10.6181
-12.743
-9.24612
-6.06:>71
-:>.1~4103
-3.78238
-2.710792
-1.b~071
K I::bI
2.4f09::>01::-1'i
1.f:H:i7211::-13
:>.67384i:::-ll()
1.362341::-07
7.:>1:>661::-106
1.6::>I!JS11::-/()4
1.';I:>92/()!::-03
.161:>111
1/2 Sn(C03}z + SOZ ~ 1/2 Sn(S03}z + COz
/JEL f( CALS)
-4653ol9
-4534.1
-4423.82
'-4351.06
-4332.45
-4379.75
-4502.74
-4711O.3~
LOG10 K
3.412b8
2.47877
1.93478
1 . 58 ~8
1.3534::'
Id9719
1.094106
1.0310105
K Ebi
258 7 . 51
301.141
06.0565
38. S3~}4
22.5656
1 5. 7468
12.4181
110.7164
1/2 Sn(C03}z + SOZ + 1/2 0z ~ 1/2 Sn(S04}z + COz
IJ!::L F< GAL,:;) )
_-45502.8
-42555.5
-39671.4
-36821 . 7
-34019.9
-3127::>.8
-28597.9
-25993.7
LOG10 K
33.374
23.2649
17.3505
13.4202
HI.6277
8.54916
6.94858
5.6842S
- 168 -
K Eb! ,
2.36613£+33
'1.84016E+23
2.241421::+17
2.63117£+13 ,
4.24334£+110
3.541311::+08
8.88342i::+06
4b333 7.
-------
TCK)
290. 1 S
400
:>100
6~10
700
6kJ~i
';i1;i0
111 kJl~)
!.
IOO
298.1S
4~JlJ
~00
601-)
7liii()
80l~
9b0
1000
TABLE XLII (Continued)
1/2 SnS + 2 SOz
Dt:L F(CAL::»
12670.6
18499.3
23958.
29223.9
34324.9
3927:2. :)
44l-j7b.LI
LIS 7 1 7. '6
~ Sz + 1/2 Sn(S04h
LOG10 K
-9.29328
-1i(;.t 13:>
- 1 0 . 4 782
-10.6::>1
-10.723
- 1 ~:' . '/35
- Hi. 7108
-HJ.653::>
K t:Q
5.'19001E-11!J
7.7009::>1::-11
3.32525E-l1
2.23338E.-11
1.8924k:/I::-l1
1.84!i:;6r.i-11
1.95J72i-11
2.22067t:-ll
1/2 SnSz + SOZ ~ SnOZ + 1. 5 Sz
Ld. I"(G'~L::»
14151.::>
U~73b.6
1(';96:.)06
89'-17.7:>
673G.0S
4340.71
179'j.r57
-895.113
- 169 -
LOGl':) K
-lb.879i<
-6.9::>977
-4.7'J:ib6
-3.26113
-2.10245
-1.18652
-.4363::>2
.19::>742
K Eli
4,.1 7~.::>6t..-ll
1.~:'97~j::>c.-07
1 . 6QIILi!clo t:: - \ij::>
S . 48 1 1 (3 i - 0 4
7.8986::>1:;-03
6.::>0844E-02
.36614
1.56943
-------
TABLE XLIII
THERMODYNAMIC VALUES FOR ZINC COMPOUNDS
Cp(T)
11:0 So A B C D
f
ZnO -83.376. 10.392 11. 704 1.2184-3 2.1788+ 5
Zn(OH}z -153.37
ZnC03 -193.68 19.685 9.2932 3.2968-2
ZnS03 -178.48 25.8 18.610 2.728 -2 2. 18 +5
ZnS04 -233.69 29.767 17.062 2.0791-2
ZnS -48.5 13.800 12. 16 1. 236 -3 1.361 +5
ZnSi03 -294.32 20.498
Note:
Positive and negative integers after values in
Columns Band D are exponents of powers of 10.
Thus, 9.16-3 is 9.16 x 10-3.
- 170 -
-------
HK)
298. 1:;)
41(11)
S0tO
60~
7\()0
!:W~
9 I!) I!)
I11JltHo
lCK)
298. 1 :>
41010
~00
6100
71tH!)
800
9100
10100
lCK)
298. 1 ~
400
:>00
61010
70(0
8010
9100
1000
lCK)
298.15
401!.1
:>~\:)
6b~;
7010
dlOlJ
~i-Wj
1 0 !(j(~
TABLE XLIV
REACTIONS OF ZINC COMPOUNDS
. -
ZnC03 + SOZ .-
lJi:L FCCAL.:)
-7274.71
-7265.67
-7589.86
-8173.1
-8979.22
-9987.8S
-11187.2
-12:>70.7
ZnS03 + COz
LOG10 K
5.33563
3.9721
3 . ~H 94 7
2.97879
2.805168
2. 73{;J15
2.11821
2.74893
K t:(,i
2 1 6:>8 6 .
9371.84
21686.74
952.343
638.386
537.223
522.65::>
5610.954
ZnC03 + SOZ + 1/2 Oz
~ ZnS04 + COz
DEL FCCAL~)
-56:361.7
-54674.9
-53160.9
-';)1717.5
-Sk.l:>lb.5
-49381.
-48364.2
-47469.3
ZnS + 2 SOz
LJI:.:L FCCALS)
1890.08
67(()0.72
11452.8
16197.6
20912 d
. 25~78. 7
31d182.1
347108.5
LO G 1 to K
41.338S
29.8905
23.2::>03
18.871
1:>.7'018
13.4'782
11.7513
110.3805
~ ZnS04 + Sz
LOG10 K
- 1 .38628
-3.66325
-5.00895
-5.90342
-6.53289
-6.99187
-7.33351
-7.58998
2 ZnS + SOZ ~ 2 ZnO
UEL FCCALS) LUG10 K
42788.4 -31.3b31
410~9.4 -22.4196
39~d9.9 -1,.~96~
37037.Y -13.~989
34~70.6 -1~.~93~
32~96.:> -b.9IiOI6
30219.1 -7.84249
2,739.3 -6.06:>97
- 171 -
K ibi
2.18022£+41
7.77161£+29
1.77931t:+23
7.4301St::+18
6.10::>1041:.+1::;
3d4891t::+13
5.64062£+11
2.40f~~£+I'='
Kt::b1
..4.1108841:.:-102
2.17146£-104
9.7961651'..-06
1.2491d5£-166
2.93166£-107
1.01889£-107
4.63973E-108
2.570511::-08
+ 1. 5 Sz
K iu
4.1;j 1 7i::-23
b ok-Jl2'J4t.-l (i
J.1699~jl:.-14
1.'c!.7797i.-l1
1.~;29~11:.-v.;';1
4.:>4473!::-vJti
!5.:.>906/i-kJ7
-------
APPENDIX III
COMPUTER PROGRAMS
- 172 -
-------
This appendix contains some of the computer programs used
in this survey.
Computer Program I is the program which lists the total file
of reference cards in order alphabetically by author and numbers
them sequentially. The last page of this program contains the
instructions for making the print-out, as described in the text
of the report.
Computer Program II is the program used to search for certain
reference nuIDbers and to arrange these in alphabetical order,
according to anyone of the other categories. Similar programs
have been written to search for references by author, date, journal,
or type of reference, as described above.
Computer Programs III and IV were used to calculate the
thermodynamics of sulfur dioxide sorption as described in Section IV
of the text. .
- 173 -
-------
FE:BRUARY 17, 1969
"
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
COMPUTER PROGRAM.I
PAGE
1
THIS PROGRAM LISTS THE FILE OF CARDS IN ORDER ALPHA8ETICALLY 8YAUTHOR,
DESCRIBED IN III IN THE GENERAL FORMAT (FORMAT 11. IT NUMBERS THEM
SEOUENTIALLY. .
DIMENSION INAME(lOI,ISH(201 .
COMMON IE SC ( 751 , 11 ( 751 , 121 75' , 13175 I , 141 75 I , 15 ( 75 J , 16 ( 75 I
CALL REREAD .
KK=O
LI NE=O
READI1,1)IPAR,INAME
1 FORMAT(A3,10A3)
READ(1,999ILAST,LDASH~KWIC,LCHECK,LBLANK
999 FORMATI5A1)
WRITE(3,ZIIPAR,INAME
2 FORMAT(lH1,25X,A3,3X,10A3,/)
J=O
C***********************************************************************
4 READ( 1,31 IESC, IREF,NUM
3 FORMAT(75Al,A4,I11
IF(NUM-9110,11,10
10 IFINUMI456,455,456
455 STOP
456 J=J+1
CALL CHANGEILAST,LDASH,KWIC,LCHECK,LBLANK,JI
GO TO 4
11 READ(99,5IIK,ISH,IREF,NUM
KK=KK+ 1
5 FORMATIA2,20A3,13X,A4,111
B02 GU TO (300,301,302,303,304,30SI,J
300 IF(LINE-42)700,700,701
701 WRlTE13,5551
555 FORMAT(lHl,1X)
LlNE=O
700 LINE=LINE+1+J
IFI11(1'-LBLANK)50,51,50
50 WRITE(3,522IKK,11
WRITE(3,81IK,ISH,IREF
GO TO 99
51 WRITE(3,523IKK,ll
WRlTE(3,81 IK,ISH, IREF
GO TO 99
301 IF(LINE-42)70Z,70Z,703
703 WRITE(3,5551
LINE=O
702 LINE=LINE+I+J
IF(ll(1)-LBLANK)60,61,60
60 WRITE(3,5Z2IKK,11
6777 IF(12(1'-LBLANKI6Z,63,62
62 WRITE(3,9)12
WRITE(3,81IK,ISH,IREF
GO TO 99
61 WRITEI3,523IKK,Il
GO TO 6777
63 WRITE(3,860IIZ
WRITE(3,81IK,ISH,IREF
C
C
C
- 174 -
-------
FEBRUARY 17, 1969
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
Computer Program I
GO TO 99
302 IFILINE-42)704,704,705
705 WRlTEI3,5~5)
Ll NE=O
704 lINE=lINE+l+J
IFIIl(1)-LBLANK)64,65,64
64 WRITEI3,522)KK,ll
7777 IFI12(1)-L~LANK)66,67,66
66 WRITEI3,9) 12
8777 IFI13(1)-LBLANK)68,71,68
68 WRlTEI3,9) 13
WRITEI3,8)IK,ISH,IREF
GO TO 99
65 WRITEI3,523)KK,ll
GO TO 7777
67 WRITEI3,860)I2
GO TO 8777
71 WRITEI3,860)I3
WRITEI3,8)IK,ISH,IREF
GO TO 99
303 IFIlINE-42)706,706,707
707 WRITE13,555)
lINE=O
706 LINE=LINE+l+J
IFlll(1)-lBlANK)72,73,72
72 WRITEI3,522)KK,ll
7888 IFI12(1)-lBlANK)74,75,74
74 WRITEI3,9)12
8888 IFI13(1)-LBLA~K)76,77,76
76 WRITEI3,9)13
9888 IF(1411)-lBlANK)7~,81,78
78 WRITEI3,9JI4
9000 WRITEI3,8)IK,ISH,IREF
GO TO 99
73 WRITEI3,523)KK,11
GO TO 7888
75 WRITE13,860112
GO TO 8888
77 WRITEI3,860)I3
GO TO 9888
81 WRITEI3,860114
GO TO 9000
304 IFIlINE-42)708,708,709
709 WRITEI3,555)
LINE=O
708 LINE=LINE+1+J
IFI11(1)-LBlANK)82,83,82
82 WRITEI3,522)KK,11
2222 IFI12(1)-lBLANK)84,85,84
84 WR 1 TE I 3,9) 12
3222 IFI13(1)-lBlANK/B6,87,86
86 WRITEI3,9)13
4222 IFI14(1)-lBlANK)88,89,88
88 WRITEI3,9)14
- 175 -
(Continued)
PAGE
2
-------
FEBRUARY 17, 1969
109
110
111
112
113
114
115
116
117
11B
119
120
121
122
123
124
125
126
127
128
17.9
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
Computer Program I (Continued)
PAGE
3
527.2 IFII5(11-LBLANK)90,91,90
90 WR I TE I 3,9 I 15
9001 WRITE(3,8)IK,ISH,IREF
GO TO 99
83 WRITE(3,523)KK,I1
GO TO 7.222
85 WRITE(3,860)I2
GO TO 3222
87 WRITE13,860113
GO TO 4222
89 WRITEI3,860)I4
GO TO 5222
91 WRITE(3,860115
(;[1 TO 9001 .
305 IFILINE-42)710,710,711
711 WRlTEI3,555)
LINE=O
710 LINE=LINE+1+J
IFII1(1)-LBLANK)100,101,100
100 WRITEI3,522)KK,I!
6222IFI12111-LBLANKI102,103,10Z
102 WRITE(3,,9112
7222IF(13(1)-LBLANK)104,105,104
104 WRITEI3,91I3
8222 IFI14(1)-LBLANK)106,107,106
106 WRITEI3,9)ILf
9222 IFII5(l)-LBLANKI108,l0'1,108
108 WR I TE I 3,9 I 15
9223IFII6(1)-LBLANK)110,111,110
110 WR IT E I 3,9) 16
9002 WRITEI3,8)IK,ISH,IREF
GO TO 99
101 WRITE(3,523)KK,11
GO TO 6222
103 WRlTEI3,860) 12
GO TO 7222
105 WRITE13,860113
GO TO 8222
107 WRITE13,860114
GO TO 9222
109 WRITE13,860115
GO TO 9223
111 WRITE13,860116
GO TO 9002
522 FORMATI1H ,13,2X,75A11
9 FORMATI1H ,5X,75A11
8 FORMATI1H ,5X,A2,12011X,A3)},lX,A4,n
523 FORMATI1H ,13,1X,75A1)
860 FORMATI1H ,4X,75A11
99 00 69 N=1,75
IlIN)=LBLANK
12(N)=LBLANK
13INI=LBLANK
I4IN)=LBLAI~K
- 176 -
-------
F~BRUARY 17, 1969
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
I
I -
Computer Program I -(Continued)
15INI=LBLANK
16INI=LBLANK
69 CONTINUE
1=20
J=O
801 L= I
800 CONT I NUE
J=O
1=0 .
IFIL-2014,888,4
888 DO 79 N= 1,75
I1INI=LBLANK
I2(NI=LBLANK
I3INI=LBLAf\lK
14(NI=LBLANK
I5(NI=LBLANK
16(NI=LBLANK
79 CONTINUE
GO TO 4
ENO
PAGE
4
- 177 -
-------
FEFIRUARY 17, 1969
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
Computer Program I (Continued)
PAGE
SUBROUTINE CHANGEILAST,LOASH,KWIC,LCHECK,LHLANK,J)
COMMO~ IESC(75),II1751,I21751,I31751,I4(751,I51751,I6(751
00 100 1=1,75
IF( IESCI I )-LASTl10,11,l(\
10IFIIESCIII-LOASHI20,11,20
20 I F I IE SC I I I -K'rI I C) 30, 11 ,30
30IF(IESCIII-LCHECKI40,11,40
40 GO TO 100
11 IESCIII=LBLANK
100 CONTINUE
GO 10 (61,62,63,64,65,661,J
61 00 661 1=1,75
IlIII=IESCIII
661 CONTINUE
GO TO 70
62 00 662 1=1,75
I2III=IESCIII
662 CONTINUE
GO TO 70
63 00 663 1=1,75
13111=IESCIII
663 CONTI NUE
GO Tn 70
64 00 664 1=1,75
14111=IESCII)
664 CONTI NUE
GO 10 70
65 00 665 1=1,75
151 I )=IESCI 1 I
665 CONTINUE
GO TO 70
66 00 666 1=1,75
161 1 1= 1 E SC I 1 I
666 CONTI NUE
70 RETURN
END
- 178 -
--
1
-------
FEBRUARY 17, i969
1
2
3
4
5
h
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
. Computer Program II
PAGE
1
C
C
C
SAMPLE 1.0. SEARCH PROGRAM - 1
GIVEN CERTAIN REFERENCE NUMBERS THIS PROGRAM WILL LIST THEEM IN
ALPHABETICAL ORDER.
DIMENSION INUMSI201,KBSI751,M(751
WRITE13,4561
456 FORMATIIH1,IXI
READll,3INUMBER
3 FORMAT! 121
REA[)(I,IIINUMS
1 FORMA TI 20A4 1
REAOIl,4ILAST,LDASH,KWIC,LCHECK,LALANK
4 FORMATI5Al)
N=O
5 READll,2IKBS,IREF,JCARD
2 FORMATI75Al,A4,Ill
IFIJCARDI8,8,68
68 DO 99 I=I,NUMBER
IFI INUMSI II-IREFI80,81,80
80 GO TO 99
81 IF(JCARO-lI20,23,21
23 N=N+ 1
21 DO 98 J=I,75
IFIKBSIJI-LASTII0,11,10
10 IFIKBSIJI-LDASH)70,71,70
70 IF(KBSIJ)-KWICI30,31,30
30 IF(KBSIJI-LCHECKI40,41,40
40 MIJ)=KASIJI
GO TO 98
11 MIJI=LBLANK
GO TO 98
71 MI J)=LBLANK
GO TO 98
31 MIJ)=LAlANK
GO TO 98
41 MIJ)=LBLANK
98 CONTINUE
IFIMIII-LALANK)60,61,60
60 WRlTEt3d2IM
12 FORMATIIH ,IX,75All
GO TO 69
61 ~JRITEI3,l3IM
13 FORMATIIH ,75Al1
GO TO 69
99 CONTINUE
IFINUMBER-NI8,8,5
8 S TOPOOI
6 READll,2)KBS,IREF,JCARD
IFIJCARD-9)108,108,1000
108 WRITEI3,54)K8S,IREF
GO TO 5
100 IFIJCARDI8,8,21
54 FORMATIIH ,IX,2Al,IX,3Al,lX,3Al,lX,3Al,lX,3Al,lX,3Al,IX,3Al,lX,
l3Al,lX,3Al,lX,49Al,2X,A4,/)
20 WRITEI3,7) .
- 179 -
~;
-------
FEARUARY 17, 1969
55
56
57
58
Computer Program II (Continued)
PAGE
7 FORMATIIHl,'FINISH ABSTRACT')
STOP003
69 GO TO 6
END
- 180 -
2
-------
COMPUTER PROGRAM III
CPARG
1018 FOR 1=1T04
200 RI::AD Tel)
300 L~l A(!)=I(I)t2
4010 LEI 8(1) = 1./1(I)t2
500 PRINT T(I),A(I),8(1)
6100 NEXT I
700 UATA 3108,4100,500,600,
8010 END
SIMI:::G4
1~0 DIM A(4,4),X(4,1),C(4,1) ,8(4,4)
200 MAT REAU A,G
300 MAT P~INT A,C
41010 MAT B=IN~(A)
. 5010 MAT X =I:!*C
61010 MAT PRINT X .
7100 DATA 1,31010,910101010,1.11111 £-5
701 DATA 1,500,25100~0,4 £-6 .
7102 DATA 1,700,491O~100,2.041O82 £-6
7103 DATA 1,9100,81101000,1.23457 £-6
784 DATA 7~10237,7.4315,7.8837,8.2129
8108 £ND .
CPCOMP
1100 READ N,A,b,C,D
21010 FOR K=1 10 N
.3100 REAU T< K)
4010 LET C(K) = A + b*T(K)
51010 PRINT T(K),C(K)
501 NEXT K
550 UATA 1,1,1,1,1
551 DATA 2
6010 END
+ C*1(K)t2 + U*T(K)t-2
- 181 -
-------
COMPUTER PROGRAM IV
lHERCu
100 OItv; T(S)
110IJIMC(18)
120 UH'I O( 18)
1 30 U I 1") G ( 1 8, 8 )
1 40 iJ I 1'1 V ( 1 8, 1 3 )
1:>0 U I ['1 H ( 1 8 )
1 60 D I rvi S ( 1 8 )
170 OIM A'fAWfIN~G vALuE::::>
290 PRINT H(I);S(I);A(I)JB(I);C(I);U(I)
31210 NEXl I
310 FOR K =1 TU N
320 FUR I = 110 M ,
330 LET Q = HCI) + ACI)*Cl'CK)-T0)+BCI>*
340 LET Q=Q+C(I).(T(K)t3-10t3)/3-I.)(I)*«I/I(K»-(I/T0»
350 LET E = S(I)+A(I)*LOG(T(K)/T0)+B(I)*(T(K)-10)
360 LET E = E+C(I)*(1(K)t2~10f2)/2-D*«I/TCK)t2>-Cl/T0t2»/2
370 LET G(I,K)=Q-1'CK)*£ '
380 NEXT I
39v) N£XT K
400 FOR J=l 10 ~
410 FOR I = 1 TO M
42vj I~EAD v( I, J)
430 i>JEXT I
440 PRINT
4~0 PkINT
460 ,PRINT "STOIC. COEr f. "
470 I"ut< 1=1 TO (vi
480 P I'd NT V ( I , J )
490 NIi:XT I
:>00 PHINI
510 Pi, = 0
540 FOt< I = 1 10 M
550 LET F(K) = FCK) + G(I,K)*VCI,J)
560 NEXT I '
:>70 LEI P(K)= -FCK)/CR*lCK)*LOGCI0»
580 LET W(K) = EXP(-FCK)/(R*T(K»)
590 PRINT T(K),FCK),PCK),WCK)
- 182 -
-------
COMPUTER PROGRAM IV (Cont'd)
- 2 -
TH£kCU CONTINUED
600 NEXT K
610 NEXT J
620 REM CONT~OL PARAMETERS M~ N~ R ~ T0 ~~
630 DATA 17
640 IJATA 8
650 DATA 1.986
660 DATA 298015
670 DATA 9
680 REM HERE ARE THE IJATA FOR THE COMMON SPECIES
690 REM H0~ SO, A~ BCT)~ CCI2)~ GCT-2)
700 REM ORDER 02, 602 ~ H20 ~ S03 ~ SI02 ~ S2 ~ G02
710 DATA 0 ~ 49.007, 5.179 ~5.24E-3 , 2.141E-6 , 41860
720 DATA -70947 ~ 59.297 ~ 7.0756 ~ 1.076£-2 , -4.848E-6~-29107
730 DATA -57798 , 45.105 , 6.9~4 , 2.569£-3 ~ 3.1~~£-7 ~ 24706
7410 UATA -94470 ~ 61.345 ~ 9.054 ~ 1.679E-~ ~ -7.659£-6 ~ -113429
750 DATA -217500~ 1~. ~ -5.364 ~ 5.413£-2 ~ -3.396E-5~257565
760 UATA 30840 , 54.51 , 7.866,1.892£-3 , 8.996E~7 , -29053
770 DATA -94035 ~ 51.125 ~ 6.94 , 9.742£-3 , 3.667E-6 ~ -57464
790 HEM HERE ARE THE DATA ON COPPER COMPOUNDS .
800 REM CuO ~ CuG03 ~ CuS03 ~ CUS04 ~ GUS
810 HEM CU20 ~ ~u2C03 , CU2S03 ~ GU2504 ~ GU2S
820DATA -39490, 10.187 ~ 9.267 , 4.797E-3 , 0 ~ 0
. .
830 DATA -142100 ~ 21.023 , 14.91 , 2.151E-2 ~ 0 , 139000
840 DATA -127280 , 25.710 ~ 16018 , 1.99£-2 , U , {2)
850 DATA -184220 , 27.067 , 18.805 , 1.718£-2 ~ 10 ,2792
860 DATA -11600 ~ 15.9 , 10.6 ,2.64E-3 , 0 , 0
87v) REt-', CUPROUS
880 DATA -40780 , 22.521 ~ 14.893 ~ S.698£-3 .. 0 ~ 0
890 DATA-142290 , 37.63 ~ 2~.S3 ~ 2.241~-2 , 0 , 1.39£+5
900 DA.fA -127060 ~ 40.60 , 21.8 , 2.08£-2 ~ 0 ~ 0
910 DATA -179510 , 38.463 ~ 24.19 , 2~.4E-2 , 0 , S8000
920 DATA -19.931 .. 28.883 , 19.492 ~ 0 ~ 6 .. 0
930 ~~M CU2S DATA (900) APPLY ONLY TO THE 2S 10 103 C ~ANG~
940 riEM HEkE AuE lHE lEMPEkATUk~~
9510 IHIJA 291:S. 1 S ~ 400 ~ S00', 6010 ~ 7160 .. 800 ~ 91610 , 101<110
960kEM STUI~HIOMEThIC COEF~ICIENTS
970 HEM STANDARD SE~uENC£ ~Ok CUPkIC Cl,I,2)
980 DATA ~j, -1~ 0, 16, Vj, 0~ I, 0~ -1, I, Vb 0,
99VJ DA.l f.\ -. ~ ~ - I, IU, ~J ~ V), {:j, 1 ~ !(j, - 1.. . (:i , 1, 10 ~
10 kJ 0 LJ A T {\ 1:1 , - :2 , b , (I) ~ 19 , 1 ~ ~j , !:i , U , b , 1, - 1 ~
1 01 ~J utl:fA 16 , - 1, (~;, [~ , 12;, 1 ~ :; , \(;, 1, {:j, U, It) , - 2,.
1020 uEM STANUAKU ~~0UENC~ FOR C0P~OU~ Cl~I,2)
11:J3b Li in. f-\ I-J, -1, (I), l:::, \:.), l;~ I~ 0, 0~ (!)~ ~'I, \.:1, 0, -I, I, ~:J, 0
1040 uF\I'A -.5, -1, ~u 0,10, Ie), 1, vj~ leu ~:J~ ~j, l(j, Ii), -1, i;j~ 1,0
IkJ50uATA 0, -2, 0, 0, 0, 1~ 10, 0, 0, 0~ 10, 0, 0~ 0, 0, 1, -1
1 f!J6eJ LJi:nA ~j~ -1, 1:), I(i, Iu, 1.::i, 0~ (~, b, 0; 0, b~ 1, (,~ 0, Ie" -2
1070 uEM K~00X INVOLVING COP~~ri
1080 uATA 0~ -1, 0, 0, 0~ 0~ ~, 0, -2, ~, ~, 0~ ~, 0, 0~ 1, 16
1 v)~0 Ei'-JD
vj ~ vi , 10, ~j ~ I::;
o , v.:, ~ I!I , vj ~ vi
!cl, VJ , U ~ \(J , ki
0, 0, 0, 0, 19
- 183 ~
-------
COMPUTER PROGRAM IV (Cont'd)
- 3 -
1-~t::GUAT
520 .k~M H0~~0~A~B~G~U~ Of EACH COMPUUND
530 kEN GP0S. H2S04 S03 H2U 02 G S02 C02 CO H2
540 DA).A -194548 ~ ~7.501 ~ 36.77 ~ 9.16E-3 ~ -2.0B8~-6 ~ -S4320~
5S~ ~ATA -94470 ~ 61.345 ~ 9.~54 ~ 1.679E-2 ~ -7.659£-6 ~ -113429
560 UA1A -57798 ~ 4~.10S ~ 6.954 ~ 2.S69E-3 ~ 3.1522-7 ~ 24706
570 UATA 0 ~ 49.007 ~ 5.179 ~ 5.24~-3 ~ -2.141E-6 ~ 41860
580 DATA 0 ~ 1.372 ~ -.221 ~ 9.963E-3 ~ -4.611E-6 ~ -27007
590 UATA -70947 ~ 59.297 ~ 7.0756 ~ 1.076£-2 ~ -4.B48E-6~-29107
600 DATA -94035 ~ 51.125 ~ 6.94 ~ 9.742£-3 ~ -3.667£-6 ~ -57464
610 uAIA -26416 ~ 41.21B ~ 5.735 ~ 2.703£-3 ~ -5.356£-7 ~ 42111
620 DATA 0 ~ 31.208 ~ 7.562 ~ -1.5£-3 ~ 1.193£-6 ~ -29332
630 HEM hEAU IN TEMPEkAluk£~ .
640 uATA 298.15 ~ 400 ~ 500 ~ 600 ~ 7~0 ~ ~00 ~ 900 ~ 1000
650 REM HEAD IN STOICHIOMETRIC COEFFICIENTS
660 OA TA - 1 ~ 1 ~ 1 ~ (9 ~ v) ~ 0 ~ 0 ~ !i') ~ 0
670 DATA 0 ~ -1 ~ 0 ~ . 5 ~ 0 ~ 1 ~ 0 ~0 ~ 0
680 DATA -2 ~ 0 ~ 2 ~ 0 ~ -1 ~ 2 ~ 1 ~ 0 ~ 0
690 VA TA -1 ~ 0 ~ 1 ~ 0 ~ - 1 ~ 1 ~ (9 ~ 1 ~ 0
700 DATA -1 ~ 0 ~ 1 ~ 0 ~ 0 ~ 1 ~ 1 ~ 0 ~ -1
710 DATA -1 ~ 0 ~ 2 ~ 0 ~ 0 ~ 1 ~ 1 ~ ~ ~ -1
720 GATA 0 ~ -1 ~ 0 ~ 0 ~ -1 ~ 1 ~ 0 ~ 1 ~ ~
730 DATA 0 ~ ~1 ~ 0 ~ 0 ~ 0~ 1 ~ 1 ~ -1 ~ 0
740 DATA ~.~ -1 ~ 1 ~ 0 ~ 0 ~ 1 ~ ~ ~ ~ ~ -1
7~0 DATA 0 ~ -2 ~ 0 ~ 0 ~ -1 ~ 2 ~ 1 ~ 0 ~ 0
800 END
BASiJAl
680 REM HERE ARt; THE DATA FOh THE GOt'iMON Sf'ECli::S
690 REM H0~ SO~ A~ 8eT)~ CeT2)~ CeT-2)
700 HEM OHDt;R02 ~ C02 ~ H20 ~ 503 ~ SI02 ~ S2 ~ C02
710 DATA 0 ~ 49.007~ 5.179 ~ 5.24E-3 ~ 2.141E-6 ~ 41860
720 DATA -70947 ~ 59.297 ~ 7.0756 ~ 1.076E-2 ~ -4.848[-6~-29107
730 DATA -57798 ~ 45.105 ~ 6.954 ~ 2.569E-3 ~ 3.152[-7 ~ 24706
740 DATA -94470 ~ 61.345 ~ 9.054 ~ 1.679[-2 ~ -7.659E-6 ~ -11342~
7~0 DATA -217S00~ 10. ~ -5.364 ~ ~.413t::-2 ~ -3.396£-5,257565
760 DATA 30840 ~ 54.51 ~ ~.B66~1.892E-3 ~ 8.996E-7 ~ -29053
770 DATA -94035 ~ 51.125 ~ 6.94 ~ 9.742~-3 ~ 3.667E-6~ -57464
- 184 -
-------
-.--.. -~ n~-
COMPUTER' PROGRAM IV (Cont'd)
- 4 -
LI/DAT
790 .REM HERE ARE THE DATA ON LITHIUM COMPOUNDS
800 REM LI20 1 LIOH 1 LI2C03 1 LI2S03 1 LI2S04
810 DATA -142500 1 9.0519 1 14.932 1 6.0776E-3 1 0 ~ 3.378E+5
820 DATA -116535 1 10.227 1 11.98 1 8.237E-3 1 0 1 2.267E+5
830 DATA -290260 1 21.582 ~ 20.57 1 2.279E-2 1 0 1 4.77E+5
840 DATA -279400 1 26.00 1 21.84 1 2.118E-2 1 0 1 3.38E+5
850 DATA -342580 1 35.357 1 24.23 1 2.362E-2 1 0 1 3.96E+5
910 REM HERE ARE THE STOICHIOMETRIC COEFFICIENTS
920 REM ACID REPLACEMENT REACTIONS
930 DATA 0 1 -1 1 0 1 0 1 0 1 0 1 1 1 0 1 0 1 -1 1 1 1 0
9413 DATA 0 1 -1 1.1 1 0 1 0 1 0 1 0 1 0 I -2 1 0 1 1 1 0
950 REM NO SILICATE DATA
960 REM OXIDATIVE REPLACEMENT REACTIONS
970 DATA -.5 1 -1 1 0 1 0 1 01 011 1 0 1 0 1 -1 1 0 1 1
980 DATA -.5 1 -1 1 1 1 0 1 0 1 0 1.0 10 1 ~2 1 0 1 0 1 1
990 REM NO SILICATE DATA
1000 REM REDOX REACTIONS ON SULFUR
11310 REM NO SULFIDE DATA
1020 REM NO SULFIDE DATA
NAIDAT
790 REM HERE ARE THE DMTA FOR SODIUM COMPOUNDS
800 REM NA20 1 NAOH 1 OA2C03 1 NA2S03 1 NA2S04 1 NA2S 1 NA2SI03
810 REM SULFATE HAS A PHASE TRANS AT 259CI H=2640
820 DATA -1028713 1 16.986 1 15.693 1 5.3968E-3 1 0 1 13
830 DATA -101910 1 27.71 1 -7.0231 1 5.54976E-2 1 -2.036E-5 1 58105~
.840 DATA -269720 1 32.49 1 16.874 1 3.2395E-2 1 0 1 0
850 DATA -260400 1 34.879 1 22.60 1 2.05E-2 1 0 1 0'
860 DATA -330640 1 35.692 1 15.533 1 5.2773E-2 1 0 1 0
870 DATA -92960 1.22.40 1 19.81 1 1.64E-3 1 0 1 0
880 DATA -362650 ~ 27.19 1 31.39 1 9.597E-3 1 0 1 6.467E+5
8913 REM
900 REM READ IN TEMPERATURES
9.10 DATA 296.15 1 400 1 500 1 600 1 700 1 800 1 900 1 1000
920 REM HERE ARE THE STOICHIOMETRIC COEFFICIENTS
9313 REM ACID REPLACEMENT REACTIONS
9413 DATA 0 1 -1 1 0 1 0 1 0 1 0 1 1 1 0 1
950 DATA 01 ' -1 1 1 1 0 1 0 1 0 1 0 1 11 1
960 DATA 0 1 -1 1 0 1 0 1 1 1 0 1 0 1 0 1
970 HEM OX mATI VE REPLACEMENT kEACTIONS
980 DATA -.5 1 -1 1 0 1 0 1 0 1 0 1 1 1 0 1 0 1 -1 1 01110 10
990 DATA -.5 1 -1 1 1 1 0 1 0 1 0 1 0 1 0 1 -1 1 0 1 0 1 1 1 0 1 0
o 1 -1- 1 1 1 0 1 (1 1 0
-2 1 0 1 1 1 (1~1 0 1 0
o 1 0 1 1 1 0 1 0 1 -1
- 185 -
-------
COMPUTER PROGRAM IV (Cont'd)
- s -
~~/0Hl CONTIN~~u
116Gb.
11';10
lEd:;
1030
1~ij0
UAIA -.j , -1 , W , 0 , 1 , 0
R£~ ~EuUX kEAC1ION~ ON ~JLF'UR
tJA "it\ 0 , - 2 , ~j , ~) , (6 , 1 ,
DATA 0 , -1 , U , 0 , 0 , 1.~
I:..NU
,~j,0,
o , 0 , i1 ,
1 , b , -1
li , (:; , 0 , ~) , tj , 1 , - 1 , 0 ,
, ~ , 2 , ~ , ~ , 0 , 0 , -~ , 0
K/DAT
79b I , 2.876 , 2.379£-2 , 0 , 4.257£+5
850 KEM DATA IN 840 GOOD ONLY 1'0 S95C CK2S04)
890 REM K£AU IN TEMPERATURES
900 UATA 298.15 , 400 , 50~ , 600 , 700 , 800 , 900 , 1000
910 ~EM HERE ARE T~E ~TOICHIOMETKIG CUE~~I~IENl~
920 REM ACID REPLACEMENT REACTIONS
930 DATA 0 , -1 , eJ , 0 ,0 , 0 , 1 , 11 , 0 , ,-1 , 1 , 0
940 REM NO OH DATA
950 kEM NO SILICATE DATA
960 REM OXIDATIVE REPLACEMENT ,KEAC1IONS
970 DATA -.5 , -1 , 0 ,0 , 0 , 0,1 , 0 , 0 , -1 , 0 , 1
980 REM NU OH DATA
990 REM NO SILICATE DATA
1000 REM REDOX H~ACTION~ ON ~UL~Jk
1010 REM NO SULFIDE DATA
1020 REM NO SULFIDE DATA
1030 END
- 186 -
-------
COMPUTER PROGRAM IV (Cont'd)
- 6 -
t.; G/ iJA T
7816 REM HEH£ AkE THE-DATA ON MAGN£SIUM COMPOUNDS
7~0 ~EM MGO , MGCOH) , MGG03 , MG~03 , MGS04 , MGS , MG~I03
~00 DATA -143630 , 6.4~25 , 10.175 , 1.7392£-3 , 0 , 1.4788£+5
810 DA'!'A -22168210,15.077,13.034,1.579£-3,16,0
820 DATA -2639816 , 15.696 , 18.613 , 1.37941::-2 , fO , 401592£+5
8316 DATA -24116160 , 22.5 , 17.09 , 1.684£-2 , 16 , 1.48E+S
8416 DATA -31655016 , 21.9 , 16.53 , 2.18£-2 , 16 , 1.578E+3
8510 DATA -83161616 , 110.6 , 9.24 , 2.51::-3 , 16 , 7.93£+2
86~ DATA -3576316 , 16.197 , 24.535 , 5.437£-3 , fO , 5.867£+5
8710 kEM
CA/UA'f
1616 k£M HERE ARE iJATA FUk CALCIUM SYSTEM.
1716 KEM CAO , CACOH)2 , CAe03 , CAS03 , CAS04 , GA~ , CASI03 ,
180 k£M CA3CP04)2
1916 REM NO DATA FOk CAHP04
2100 DATA -151730 , 9.484 , 11.857 , 1.0798E-3 , (() , 1660416
210 DATA -235600 , 19.924 , 25~131 , 2,8822E-3 , 16 , 45167816
220 DA1A -288110 , 22.194, 24.965 , 5.~37E-3 , 16 , 6197160
230 DATA -275880 , 24.201 , 18.770 , 1.618£-2 , fa , 16610016
240 DATA -34161916,25.491,17.220,2.337£-2,16,325616
2516 DATA -1153616,13.5,10.2,3.8£-3,10,16
2616 DATA -37741616 , 216.9, 25.B5 , 3.94£-3 , 0 , 5650016
2716 UATA -98621616 , 57.6 , 48.24 , 39.68£-3 , 16 , 500161616
280 END
- 187 -
-------
COMPUTER PROGRAM IV (Cont'd)
- 7 -
BA/ DA T
790 HEM HEkE AHE THE DATA ON bAHIJM COMPOUND~
800 ~£M bAD, UACOH)2 , BAC03 , BA503 , BA~04
810 DAIA -132070 , 16.795 , 12.733 , 1.(I)392E-3 , 10 , 198290
8.20 DATA -2260210,12.613, 16.9I(J,21.90E-3, 0,0
830 DATA -2871610 , 26.781 , 210.76 , 1.1694i-2 , 10 , 477\!)B\!)
8510 DATA -28261010 ,28.60 , 19.64 , 1.614£-2 , 0 , 19810010
8610 DATA -3499910 , 31.487 , 33.7~9 , 3.401£-3 , 10 , 8394010
8910 HEM TEMPEHAT~kES .
9010 DATA 298.15 , 41010 , 50~ , 6100 , 700 , 81010 , 9010 , 1101010
919 REM STOICHIOMETRIC COEFFICIENTS
939 REM REPLACEMENT HEACTIONS
9610 HEM OXIUATIVE REPLACEMENTS
970 DATA -.5 , -1 , 1 , 0 , 10 , 10 , 10 , 10 , -1 , {IJ , 0 , 1
989 DATA -.5 , -1 , 10 , 10 , 10 , 10 , 1 , 10 , 10 , -1 , 10 , 1
981 DATA (6 , -1 , 0 , to , 0 , 0 , 1 , '1 , ((} , -1 , 1 , 10
982 DATA ~ , -1 , 1 , Ii') , 10 , Iii , 0 , 0 , -1 , 10 , 1 ,0
9910 END
i'H'IJ/uAT
790 REM HERE AkE THE DATA ON MANGANE~E +2 AND ;3
800REM MNO , MNCC03) , MN~03 , MNS04 , MNS , MN~I03
8110 REM MN203 , MN2CC03)3 , MN2CS03)3 , MN2C~04)3
8210 HEM MANGANOUS .
840 DATA -919310 , 14.265 , 11-104 , 1.94£-3 , Iii , 879010
8S0DATA -213740 , 20.474 , 21.99 , 9.3g-3 , Iii , 469S00
8610 DATA -1973710 , 24.410 , 18.~1 , 1.704£-2 , 0 , 8~000
870 DAtA -253950 , 26.781 ,"29.241 , 8.916~-3 , 0 , 703800
88fJ DATA .-49452 , 18.682 , 11.396 , 1.799i.-3 , 0 , .0
890 UATA -3~221~ , 21.2KJ6 , 26.398 , 38.77~-J , 0 , 6.1~6E+~
9~b Hi.M ivjf.)i\!G?)NIL;
910 UA1A -229110 , 26.398 , 24.726 , H.376~-3 , ~ , 32~800
920 UAlA -S4j460 , 44.6 , 41.65 , 5.851£-2 , 0 ; 740000
930 uA~A -502390 , 53.6 , 4~.46 , S.368[-2 , 0 , 323000
940 DATA -666900 , 61.7 , ~2.63 , 6.16~-2 , 0 , 497000
';;1::>[; j,I~;."; Hl::hl:: Aht: "lrli Ti.hI"l::KA1Ui,ES
960 UATA 29b.1~ , 4~W , ~0U , 600 , 700 , bG0 , 90~ , 1~00
97\') r;£::(vj
980 kt:M S10ICHIaMi.T~IC COEFFICIENTS
9916 i~t.:(>'J I/JANGANOJ~
10~~ UAIA ~,-1,0,0,0,0,1, 0,-1,1,0,0,~, 0,0,16,0
1010 uA1A 0,-1,0,0,1,0,0, 0,0,1,16,0,-1, 0,0,0,~
102~ DATA -.5,-1,0,16,0,0,1, 0,-1,0,1,0,0, 0,~,0,0
- 188 -
-------
i--- ---
COMPUTER PROGRAM IV (Cont'd)
- is -
i"IN/iJA'j" CON'i'Ii'JUil.i
.
1030
1040
1 v..;jfj
1060
1070
10810
10910
1100
1110
1140
I.iA1A -.~,-1,0,0,1,0,0, 0,0,0,1,0,-1, 0,0,0,0
UATA 0,-2,0,0,0,1,0, 0,0,0,1,-1,0, 0,0,0,0
uATA 0,-1,0,0,0,1.~,0, 2,0,0,0,-2,~ ,0,0,10,0
j"(t:I'1 ("jANGAI\i I C
DATA 0,-1,0,0,0,0,1, 0,0,0,0,0,0, 0,-.3333,.3333,0
uATA -.5,-1,0,0,0,0,1, 0,0,0,0,0,0, 0,-.3333,0,.3333
DATA 0,-2,0,0,0,0,3, 0,0,1,1,0,0, 0,-1,0,0
UATA -.5,-2,0,0,0,0,3, 0,0,0,2,0,0, 0,-1,0,0
DATA 0,-1,0,0,0,0,0, -2,0,0,4,0,0, 0,0,0,-1
END
F E/ uA T
790 f
800 REM FEO , FEC03 , FE~03,Fi::~04 , ~i::S , ~iSI04
810 REM Fi203 , FE20 DATA -165540 , 2::>.3 ,18.:>7 , 1701E-2 , kJ, 76000
860 UATA -2204110 , 2::>.682 , 20.96 , 1.974E-2 , 0 ~ 134000
870 DATA -22800 , 1:>.2 , 12.2 , 2.38£-3 , 0 , 0
875 DATA -343540 , 35.38 , 36.51 , 9.36£-3 , (2) , -67000-0
880 HEM ADDITIONAL UATA AVAILA~LE FOrt 870 A80VE L3SC
890 REM FEkklG DATA .'
900 DATA -196420 , 20.88 , 23.48 , 1.859£-2 , 0 , 354800
910 DATA -502660 , 44.8 , 40.4 , 6.872i-2, 0 , 7.72£+5
920 DATA -4~74~0 , :>3.8 , 44.21 , 6.389£-2 , 0 , 35~000
930 DATA -615600 , 61.90 , 51.38 , 7.1BIE-2 , 0 , 529000
940 HEr" P¥kITi::
9:>0 DATA -42450 , 12.70 , 18.0 , 1.182£-3 , ti:J , 3.12E+5
960 kEM kEAD IN TEMPEkATUkE~
970 DATA 298.15 , 400 , 500 , 600 , 700 , 800 , 900 , 1000
980 kEM STOICHIOMETkIC COEFFICIENTS
990 kEM FERROUS, STANDARD FORM 2,2,2
1000 DATA 0,-1,0,0,0,0,1, 0,-1,1,0,0,0, 0,0,0,0, 0
1010 DATA 0,-1,0,0,.5,0,0, 0,0,1,0,0,-.5, 0,0,0,0, 0
1020 DATA -.5,-1,0,0,0,0,1, 0,-1,0,1,0,0, 0,0,0,0, 0
1030 DATA -.5,-1,0,0,.5j0,0, 0,0,0,1,0,-.5, 0,0,0,~, 0
1040 DATA 0,-2,0,0,0,1,0, 0,0,0,1,-1,0, 0,0,0,0, 0
1050 DATA 0,-1,0,0,0,1.5,0, 2,0,0,0,-2,0 ,0,0,0,0, 0
1060 REM FERRIC -- STANDARD FORM 1,1 .
1070 DATA 0,-1,0,0,0,0,1, 0,0,0,0,0,0; 0,-.3333,.3333,0i
- 189 -
1.
o
-------
.
COMPUTE,R PROGRAM IV (Cont' d)
- 9 -
FElUAT CONTINUEU
1 0810
110910
11010
11110
1120
1130
1140
DATA
DATA
DATA
DATA
UATA
iJA'i'A
ENIJ
-.5,-1,0,0,0,0,1, 0,0,10,10,10,10, 10,-.3333,10,.3333, 10
0,-2,0,0,0,0,3, 0,10,1,1,0,0, 10,-1,10,10, 10
-.5,-2,6,0,10,/0,3, 0,10,10,2,0,/0, 0,-1,0,/0, 0
0,-1,10,10,10,10,10, -~,0,1O,4,1O,0, /0,0,10,-1, /0
0,-2,10,0,10,1.5,10 ,10,10,10,1,0,10, 10,10,0,10, -1
10,-1,/0,0,10,2.5,10, 2,10,10,10,10,0, 0,10,10,10, -2
NIl DA T
7910 K~M HEK~ ARE THE DATA ON NICKEL +2 NO +3 DATA
81010 REM NIO , NISU3 , NIS04 , NIS ,
810 DATA -57264 , 9.078 , 11.176 , 2.0187£-3 , ~ , -3.8893£-5
82/0 uATA -155860 , 25.4 , 27.6~ , 7.28£-3 , 10 , -~8000
830 DATA -218500 , 18.586 ,30.078 , 9.917£-3 , 10 , 0
8410 DATA -174810 , 16010 , 9.245 , 12.795£-3 , 10 , 11
860 REM H£RE ARE THE TEMPEkATlhES
8710 DATA 298.15,41010,5100,6100,700,800,900,1000
880 REM H~R£ ARE THE STOICHIOM~tRIC MULTIPLIERS <0,0,2)
8910 DATA 0 , -2, 0, 10 , 10, 1 , 0 , 0 , 10 , 1 , -1
900 DATA I{) , -1 , 10 , 10 , 10 , 1.5 , 0 , 2 , 10 , 10 , -~
9 H!J ENIJ
CO/DAT
790 j':£1'1 HERE ARE THE DATA FOR COBALT
800 REM COO, COC03 , COS03 , COS04 , COS --NO CO+~
8110 OATA -57073 , 12.655 , 11.534 , 2.042£-3 , 10 , -39896
820 ,DATA -1733010,21.99 ,17.17 , 1.875E-2 , 10 , 99000
830 DATA -161750 , 25.5 , 18.44, 1.714E-2 , 0 , -40000
840 DATA -207340 , 27.067 , 30.095 ~ 9.91SE-3 , 0 , 691.5
850 UA1A -22760 , 16.18 , 10.S952 , 2.51E-3 , 0 , 0
b70 HEM TEMPEKATUkES
88~ DATA 298.15 , 400 , 500 , 600 , 700 , 800 , 900 , 1000
930 REM kEPLACEMENT REACIION~
940 uATA 0 , -1 , 0 , 0 , ~ , 0 , 1 , 0 , -1, 1 , 0 , 0
"'- 190 -
-------
COMPUTER PROGRAM IV (Cont 'd)
- 10 -
~O/UAT GU~TINUEO
950k~M OXluAIl~i KifLAGiM~NTS
96~ UAIA -.5 , -1 , 0 , 0 , ~ , b , 1 , ~ , -1 , 0 , 1 , 0
97lj Ht:I'j J-IEUOX Oi-.i SULFUt<
980 OAT A 0 , -2 , 0 , 0 , 0 , 1 , 0 , 0 , 0 , 0 , 1 , -1
990 DATA 0 , -1 , 0 , 0 , 0 , 1.5 , 0", 2 , 0 , 0 , 0 , -2
GtJ/iJl-\T
790 r:t:.:l'1 HERE: Ar(iJ5 , 1.718E-2 , 0 , 2792
8:50 UAIA -116Co0 , 15.9 , lr~.6 , 2.641::-3 , b , 0
855 KE:rvi CUPROUS
860 UATA -407B~ , 22.521 , 14.893 , S.69bE-3 , 0
870 UAIA-142290 ,37.63 ,20.53,2.241£-2 , 0 ,
880 uATA -12706~ , 40.60 , 21.~ , 2.08E-2 , 0 ,
890 uATA -179510 , 38.463 , 24.19 , 23.4£-2 , 0
9~0 DA)"A -19.931 , 28.~63 , 19.492 , 0 , ~ , 0
910 Kb:i"J CLJ2S DATA (9YJ~) Af'PL Y Oi\JL Y "iLJ '1 Ht: 25 lO 1IJ3 C t(.ANG~
911 kfM TEMFEriATukES "
912 DATA 298.15 , 4~0 , 500 , 600 , 100 , 8~0 , 900 , 1000
920riEM ::;TOICHIOM£TRIC CO£~~"I~1b:N1S
930 REM 31U SE0UENC£ FOH GuPKIC 1,1,2
940 DATA 0, -1, (0, tj, ~, I!J, 'I, I~, -1, 1, 10, 0,
9:>0 DATA -.5, -1, VJ, (j, 0, 0, 1, 0, -1, 0 ,1, 0,
960 DATA 0,-2,0,0,0,1, 0, ~j, 0, 0,1, -1,
970 UATA 10, -1~ 0, 0, 0, 1.5, 0, 1, 0, 0, 0, -2,
980 HEM SID SE~tJENGE FOR CUPriOUS
990 DATA 0, -1, 0, 0, 0, 0, 1, 0, 0, 0, 0, 0, 0, -1, 1, 0, (O
10100 DJ~TA -.5, -1,16,10,0,0,1, 0,10,0,10,0, "0, -1, 10,1,0
lliJ10uATA 10, -2, 0, 0, 0, 1, 0, 0, 0, 0, 0, 0, 0, Ii), (O,' 1, -1
1020 DATA 0, -1, 10, 0, 0, 1.5, 0, 0, 0, 0, 0, 0, 1, 0, 0, 0, -2
1030 REM REDOX INVOL~ING COPPER "
1040 DATA 0, -1, 0, 0, 0, 0, 2, 0, 72, ~, 10, 10, 0, 0, 0, 1, 10
1050 END
, 0
1.39£+5
k)
, 580bld
0, kJ, 0, 0, 10
" 0, 0, 10, 0, 10
0, 10, 0, 0, 0
0, 0, 0, 0, 10
- 191 -
-------
COMPUTER PROGRAM IV (Cont'd)
- 11 -
SN/ IJA T
790 .H~M HEHE AkE THE IJATA ON TIN +2 AND +4
800 H~M ~rANNOUS SNO , SNS
810 uATA -68325 , 13.555 , 9.5464 , 3.4975£-3 , 0 , 0
820 DATA -24320 , 18.395 , 8.4795 , 7.428~-3 , 0 , 95260
830 REM STANNIG SN02 , SNS2 '. SNCC03)~ , SMCS03)2,SNCS04)2
840 DATA -138750 , 12.504 , 17.652 , 2.39b6~-3 , 0 , 515790
850 UATA -39896 , 20.380 , 15.510 , 4.197~-3 , 0 , 96.3
860 DATA -330040 , 33.9 , 2~.94 , ~.5b~-~ , 0 , 794000
870 DATA -29536~ , 42.9 , 31.48 , 3.26£-2 , 0 , 5.16£+5
880 UATA -393400 , 37.1 , 36.26 , 3.788E-2 , 0 , 632000
885 HEM HEKE ARE THE TEMPEHATUH~~
890 DATA 298.15 , 400 , 500 , 600 , 700 , 800 , 900 , 1000
900 HEM STOICHIUMETRIC COEFFICIENTS
910 K£M STANNOUS
920 DATA 0 , -1 , 0 , 0 , 0 , 1.5 , 0 , 2 ,-2 , 0 , 0 , 0 , 0 , 0
930 KEf"! STANNIC
940 DATA 0 , -1 , 0 , 0 , 0 , 0 , 1 , 0 , 0 , 0 , 0 , -.5 , .5 , 0
950 DATA -.5 , -1 , 0 , 0 , 0 , 0 , 1 , 0,0, 0 , 0 , -.5 , 0,.5
960 DATA 0 , -2 , 0 , 0 , 0 , 1 , 0 , 0 , 0 , 0 , -.S , 0 , 0 , .~
970 DATA 0 , -1 , 0 , 0 , 0 , 1.5 , 0 , 0 , 0 , 1 , -1 , 0 , 0 , 0
980 END
i:N/ DA T
790 i
------- |