EPA-AA-SDSB-82-3
Technical Report
Conversion of Ammonia
Plants to Methanol Production
by
Daniel P. Reiser
February 1982
NOTICE
Technical Reports do not necessarily represent final EPA decisions
or positions. They are intended to present technical analysis of
issues using data which are currently available. The purpose in
the release of such reports is to facilitate the exchange of tech-
nical information and to inform the public of technical develop-
ments which may form the basis for a final EPA decision, position
or regulatory action.
Standards Development and Support Branch
Emission Control Technology Division
Office of Mobile Source Air Pollution Control
Office of Air, Noise and Radiation
U.S. Environmental Protection Agency
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Summary
This report investigated the technical feasibility and cap-
ital cost of converting an ammonia plant to a methanol plant, both
using natural gas as a feedstock. It was determined that the
ammonia industry, which currently produces about 20 million tons
of ammonia per year in the U.S., could convert their facilities to
produce 16.4 million tons per year of methanol, or a fuel oil
equivalent of 150,000 barrels per day. Such a conversion would
cost about $2.1 billion, compared to a cost of 4>3.1 billion for
building new natural gas-based methanol plants of the same capac-
ity. While converting ammonia plants to methanol production has
favorable capital costs over that of building new plants, the sav-
ings of one-third is not large, particularly considering the
effects of eliminating (or reducing) ammonia production. Thus, it
would appear at this time that large savings cannot be obtained
from the conversion of ammonia plants to methanol production.
Conversion of Ammonia Plants to Methanol Production
The U.S. ammonia industry currently produces over 20 million
tons of ammonia,[1] primarily for use in the fertilizer industry.
Ammonia is also used as the starting point of most military
explosives, and it touches some aspect of nearly all other indus-
tries in the U.S. [2] Methanol is also an important product of the
U.S. chemical industry, and with a growing interest in methanol as
a transportation fuel, an increase in its production may become
even more desirable in the future. Although ammonia and methanol
appear to be chemically dissimilar, both compounds can be com-
mercially synthesized from the same feedstock, which is primarily
natural gas. With future demand of methanol possibly escalating,
an investigation may be necessary to evaluate the feasibility and
the cost of converting an existing natural gas based ammonia plant
to the production of methanol.
Although ammonia appears to be substantially different in
chemical composition from methanol, much of the commercial synthe-
sis process is very similar for the two chemical compounds. Both
can be synthesized from the same feedstock which is primarily
natural gas, to produce the large amounts of hydrogen needed. The
major difference between these two commercial syntheses is that in
ammonia production, all carbon containing gases (particularly car-
bon monoxide and carbon dioxide) are removed so that only nitrogen
and hydrogen remain to react, while in methanol synthesis, a con-
siderable amount of carbon monoxide is retained along with the
hydrogen and no nitrogen is allowed to enter the system.
This report will analyze and discuss the feasibility and the
cost of converting an ammonia plant to production of methanol.
The first section of this report will outline the major steps
involved with the established industrial production of ammonia.
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In the section following this, the conversion of an ammonia plant
to a methanol plant will be examined. This report will then
determine the total potential U.S. capacity of methanol production
from converted ammonia plants, and the cost of this conversion on
a plant basis and a nationwide basis.
I. Description of the Commercial Production of Ammonia[2,3]
The overall commercial synthesis of ammonia involves the
reaction of nitrogen from air and hydrogen from natural gas at a
ratio of 1:3 at high pressure and relatively low temperature in
the presence of a catalyst. This overall chemical reaction is:
1/2 N2(g) + 3/2 H2(g) = NH3(g)
A typical flow diagram for the commercial production of
ammonia is shown in Figure 1. As was mentioned above, natural gas
is at present the most common feedstock used for production of
ammonia. The basic steps shown in Figure 1 for converting natural
gas into ammonia will be discussed in this section. These steps
are desulfurization, primary and secondary reforming, shift
conversion, carbon dioxide removal, synthesis gas purification,
and ammonia synthesis and recovery.
In the first step, natural gas (which is essentially methane)
is introduced and desulfurized. Much of the feed natural gas, or
methane, is contaminated with sulfur-containing compounds which
may poison catalysts downstream in the ammonia synthesis process.
Desulfurization involves the absorption of sulfur-containing com-
pounds (which is usually in the form of hydrogen disulfide) onto
activated carbon or zinc oxide. After desulfurization, the
purified natural gas is ready for reacting in the next steps of
steam reforming.
As shown in Figure 1, the steam reforming steps of the pur-
ified natural gas feedstock is carried out in two catalytic
reaction stages. The first stage is called the primary reformer,
where the methane is mixed with superheated steam and reacted over
a catalyst to produce a partially reformed gas, consisting of
carbon monoxide, hydrogen and unreacted methane. The overall
reaction of the primary reformer is:
CH4 + H20 = CO + 3 H2 (Primary reforming)
Primary reforming is carried out in a furnace to accomodate the
large heat transfer required. The exit gas temperature is about
750°-850°C and pressure is about 415-515 psig. The type of
catalyst used depends on the temperature and pressure in the
primary reformer.
The next step is the secondary reformer where the reforming
reaction is carried out to completion (all of the methane reacted)
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NATURAL GAS
SHIFT
CONVERSION
CO
Figure 1
Ammonia Plant Flow Diagram
STEAM
DESULFURIZATION
PRIMARY REFORMER
CH. + H00 = CO + 3H.
42 2
CO.
t
CO,, REMOVAL
METHANATION
CO + 3H = CH +
AIR
SECONDARY REFORMER
CH. + 1/2 CL = CO + 2H
! i
COMPRESSION
AMMONIA SYNTHESIS
+ 3 Hr
- 2NH,
AMMONIA
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also with a catalyst. As shown in Figure 1, sufficient air is
added to the secondary reformer, serving a dual purpose. First,
the combustion of methane and oxygen provides heat, which is used
to react the remaining methane and steam to form more carbon
monoxide and hydrogen. Second, nitrogen (via the air) is also
added to the system in the amount required later in the ammonia
synthesis process. This amount of air is adjusted to eventually
supply a hydrogen/nitrogen ratio of 3:1. A nickel catalyst sup-
ported on alumina is generally used in the secondary reformer.
Thus, while the primary reformer is used for reforming methane
only, the secondary reformer is used for both completing the
reforming process and providing the necessary nitrogen required
later in ammonia synthesis. The overall reaction involved in the
secondary reformer is:
CH4 + 1/2 02 + 2N2 = CO + 2H2 + 2N2
After the primary and secondary reformers, the next step of
CO shift conversion is applied as shown in Figure 1. CO shift
conversion utilizes the water-gas shift reaction and produces
hydrogen from carbon monoxide via the following reaction:
CO + H20 = C02 + H2 (Shift reaction)
The bulk of the carbon monoxide is first shifted to carbon dioxide
in a high temperature shift converter (HTS) operating at 350°-
450°C. The gases are then cooled and most of the remaining carbon
monoxide from the HTS is shifted to carbon dioxide in a lower
temperature shift converter (LTS) at a temperature of about
200°-250°C. The HTS catalyst consists mainly of iron oxide and
chromium oxide. The LTS catalyst consists of copper oxide sup-
ported on zinc oxide and alumina.
The effluent gases leaving the LTS converter from the shift
conversion step thus contain carbon dioxide which must be removed
or it will poison catalysts used in later steps. Most of the
carbon dioxide is removed in the bulk removal step (as shown in
Figure 1), where it is reduced to trace amounts. In removing the
carbon dioxide, scrubbing with an gaseous solution of mono-
ethanolamine (MEA) or a hot solution of potassium carbonate is
standard. Activated carbon may also be used as a means to remove
carbon dioxide.
After bulk carbon dioxide removal, methanation is applied,
where any residual carbon monoxide and carbon dioxide are con-
verted to methane, since any carbon, oxygen, or oxygen-containing
compounds poison the ammonia synthesizing catalyst in the last
step of the ammonia synthesis process. Methanation, which is
essentially the reverse of the reforming reactions, involves the
following two reactions:
CO + 3H2 = CH4 + H20
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C02 + 4H2 = CH4 + 2 H20
Temperatures are typically in the range of 300-400°C and the
catalyst is usually nickel supported on alumina, kaolin, or cal-
cium aluminate cement.
After this step, the carbon monoxide and carbon dioxide
content of the treated gas is only a few parts per million and
does not affect the remainder of the ammonia synthesis process.
However, the methane itself contains carbon and must be elimi-
nated. A cryogenic purifier system (which is not shown in Figure
1 as a distinct unit) is then used to remove all of the water and
nearly all the methane. In this unit the gas from methanation is
first dried to a very low dew point, then cooled and expanded in a
turbine to liquefy a portion of the gas. After further cooling,
the vapor from the partially liquified stream is scrubbed in a
rectifying column to remove the required amount of the methane.
The synthesis gas is now ready for the final step of compres-
sion and ammonia manufacture in the synthesis loop. This is shown
as the compression ammonia synthesis unit in Figure 1. The
reaction is:
N2 + 3H2 = -2NH3
The operating pressures for most synthesis loops fall in the range
of 150-200 atm (2200-2940 psig). This final step involves a
catalyst which generally consists of iron with the addition of
oxides of aluminum and potassium. Unreacted gases are recycled.
In almost all plants ammonia is recovered by condensation. This
requires refrigeration, normally provided by the synthesis ammonia
itself. Inerts entering the system are normally removed with a
purge stream.
II. Conversion of an Ammonia Plant to Methanol Production[2,3]
Commercial synthesis of methanol involves the reaction of
carbon monoxide and hydrogen, both which can be obtained from a
natural gas feedstock, at an overall ratio of 1:2. High tempera-
tures and pressures are used, in addition to a catalyst to speed
up the reaction. The overall reaction is:
CO + 2H2 = CH3OH
A flow diagram representing a typical commercial methanol
production process is shown in Figure 2. When comparing Figure 2
to the ammonia plant flow diagram of Figure 1, it can be seen that
the initial steps of both processes are similar. However, meth-
anol production also involves additional steps which replace many
of the steps involved with ammonia production. The basic steps
shown in Figure 2 for production of methanol from a converted
ammonia plant are desulfurization, steam reforming, compression,
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Methanol Flow Diagram From Converted Ammonia Plant
NATURAL GAS
CRYOGENIC UNIT
DESULFURIZATION
STEAM
SULFUR GUARD
BEDS
STEAM REFORMER
CH, + H.O = CO + 3H
42 L
METHANOL SYNTHESIS
CO,
COMPRESSION
METHANOL
CO + 2H = CH OH
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cryogenic purification, final sulfur removal, and methanol synthe-
sis. These steps will be discussed below.
The first step of methanol production is the desulfurization
of natural gas, which was also the first step of ammonia produc-
tion. As with ammonia production the natural gas used for
methanol production must be processed free of sulfur to prevent
poisoning catalysts downsteam. After desulfurization the next
step is steam reforming again similar to ammonia production. For
methanol production, only one reformer is typically used which
also involves the introduction of steam, as shown in Figure 2. In
the reformer unit, the steam and methane react to form carbon
monoxide and hydrogen, identical to the reaction occurring in the
primary reformer for ammonia production. This reaction is
expressed as:
CH4 + H20 = CO + 3H2
The steam reformer in methanol production produces a carbon
monoxide:hydrogen ratio of 1:3, while methanol synthesis requires
only a 1:2 ratio. Thus, as shown in Figure 2, carbon dioxide is
added to produce carbon monoxide and consume hydrogen via the
reverse of the water gas shift reaction discussed above.
The steps following the steam reformer in methanol synthesis
differ from that found in ammonia synthesis. First of all, the
secondary reformer the carbon monoxide shift converters and the
carbon monoxide removal unit are unnecessary for methanol produc-
tion. Also, the process of methanation in an ammonia plant is
also eliminated in methanol production, because it is desired to
retain as much carbon monoxide as possible.
However, there are additional steps in the production of
methanol which are not present in the production of ammonia. The
first step is the compression of carbon monoxide and hydrogen that
has exited from the reformer. This step improves the conversion
of these reactants in the methanol synthesis unit. A turbo-driven
centrigual compressor is usually used to compress the carbon
monoxide:hydrogen mixture from about 150 atm to 300 atm. Fol-
lowing the compression step, nearly all of the carbon dioxide and
steam left are removed in a standard cryogenic feed purification
unit. A new cryogenic unit must be installed since a higher pres-
sure is used for methanol synthesis than is used for ammonia
synthesis. A second cryogenic unit is also necessary to separate
the dry, carbon dioxide-free gas into synthesis gas (H2/CO ratio
= 2, CH^ + N2 about 1 percent) and a tail gas which is used as
fuel gas and consists mainly of unreacted methane with some carbon
monoxide. The cryogenic units are shown together in Figure 2.
Following the two cryogenic units, the synthesis gas is
heated and passed through a zinc-oxide sulfur-guard bed for final
removal of hydrogen sulfide and other sulfur-containing com-
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pounds. After this comes the methanol synthesis where a new
reactor (again because of higher pressures than ammonia synthesis)
is required. The final reaction taking place in the reactor is:
2H2 + CO = CH30H
The methanol is subsequently cooled and condensed. Most of the
synthesis gas passing through this unit is not converted to
methanol and is recycled and mixed with fresh, incoming synthesis
gas.
In summary, the following units must be added to an ammonia
plant to convert it to methanol production: the compression unit,
two cryogenic units, the sulfur guard bed units, and the methanol
synthesis unit.
III. Capacity for Methanol Production
The above section described the steps involved with conver-
sion of an ammonia plant to methanol production. This section
will estimate the nationwide capacity of methanol production from
converted ammonia plants.
The nationwide capacity of methanol production from a con-
verted ammonia plant depends upon two factors. First, the ratio
of methanol to ammonia produced must be determined, based on an
equal amount of natural gas feed. Second, the current nationwide
production capacity of ammonia must be determined. These two
factors will be examined below.
The ratio of methanol to ammonia production can be based on a
stoichiometric estimate which assumes the same amount of natural
gas feedstock in both cases. For ammonia synthesis, the limiting
factor is the production of hydrogen which results in the produc-
tion of about 4.86 tons of ammonia for every ton of methane feed.
For methanol synthesis, the limiting factor is the production of
carbon monoxide which results in the production of about 4 tons of
methanol for every ton of methane feed. Thus, on this basis the
ratio (by weight) of methanol to ammonia production capacity is
0.82.
Now, the total ammonia production capacity for the U.S. must
be estimated. Current (1981) U.S. ammonia production capacity
should be close to 20 million tons based on an estimate by a
recent report on the ammonia industry.[4] In that report, 1981
ammonia production estimates are broken down by each ammonia
producing company and location, and are based on actual February
1979 production data. There are 81 plants in operation in the
U.S. producing these 20 million tons annually.[4] The producers
of this ammonia and the locations of their plants are shown in
Table l.[4]
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Table 1
1981 Ammonia Production Capacity*
Company
Agrico Chemical Co.
Air Products & Chem-
ical Co.
Allied Chemical Corp
American Cyanamid Co
Amoco Oil Co.
Apache Powder Co.
Atlas Chemical Co.
Beker Industries
Borden Chemical Co.
Camex, Inc.
Car-ren
CF Industries, Inc.
Chevron Chemical Co.
Columbia Nitrogen
Diamond Shamrock
Dow Chemical
E. I. DuPont de
Nemours
Location
Blytheville, AR
Donalds onville, LA
Verdigris, OK
New Orleans , LA
Pace Junction, FL
La Platte, NE
Hopewell, VA
Helena, AR
Fortier, LA
Fortier, LA
Texas City, TX
Benson, AZ
Joplin, MO
Conda, ID
Geismar, LA
Borger, TX
Columbus, MS
Donalds onville, LA
Donalds onville, LA
Donalds onville, LA
Donalds onville, LA
Fremont , NE
Terre Haute, IN
Pascagoula, MS
Fort Madison, LA
El Segundo, CA
Augusta, GA
Dumax, TX
Freeport, TX
Beaumont, TX
Victoria, TX
1,000 Tons Per Year
407
468
840
210
100
172
340
210
340
240
522
15
136
100
340
400
375
375
420
420
48
150
510
105
20
510
160
115
340
100
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Company
El Paso Products
Farmland Industries
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Table 1 (Cont'd)
1981 Ammonia Production Capacity
Location
Odessa, TX
Fort Dodge, IA
Dodge City, KS
Hastings, NE
Enid, OK
Lawrence, KS
Pollock, LA
Farmers Chem-CF Ind.
Felmont Oil Corp.
First Miss Corp.
FMC Corp.
Gardinier, Inc.
Georgia Pacific
Grace-Okla. Nitrogen
W. R. Grace & Co.
Green Valley Chemical
Hawkeye Chemical
Hercules, Inc.
Hooker Chemical Co.
International Minerals
& Chemicals
Jupiter Chemical (Terra)
Tyner, TN
Olean, NY
Fort Madison, IA
S. Charleston, WV
Tampa, FL
Plaquemine, LA
Woodward, OK
Woodstock, TN
Creston, IA
Clinton, IA
Louisiana, MO
Tacoma, WA
Sterington, LA
Lake Charles, LA
Kaiser Agricultural Chemicals Savawnnah, GA
Mississippi Chemical
Corp.
Monsanto Co.
NJ Zinc-Gulf and Western
Yazoo City, MS
Pascagoula, MS
Luling, LA
Palmerton, PA
1000 Tons Per Year
115
210
210
140
840
340
420
170
85
365
24
120
196
400
340
35
138
70
23
400
78
150
393
175
850
35
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Company
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Table 1 (Cont'd)
1981 Ammonia Production Capacity
Location
N-Ren Corp. (Cherokee N) Pryor, OK
N-Ren Corp. (St. Paul Ammonia) East Dubuque, IL
Occidental Chemical Co.
Olin Corporation
Pennwalt Chemical Corp.
Philips Pacific Chemicals
PPG Industries
Reichhold Chemicals
J. R. Simplot
Tennessee Valley Authority
Terra Chemicals
Triad Chemical
Union Oil Co7
U.S.A. Petrochem Corp.
USS Agri-Chemicals
Valley Nitrogen Producers
Vistron Corp.
Vulcan Materials
Wyeon Chemical Co.
Total
Taft, LA
Lathrop, CA
Plainview, TX
Lake Charles, LA
Portland, OR
Beatrice, NE
Natrium, WV
St. Helens, OR
Pocatello, ID
Muscle Shoals, AL
Port Neal, LA
Donaldsonville, LA
Kenai, AK
Brea, CA
Ventura, CA
Clairton, PA
Cherokee, AL
Geneva, UT
El Centre, CA
Lima, OH
Witchita, KS
Cheyenne, WY
1000 Tons Per Year
94
238
90
160
52
490
8
210
50
90
108
Ik
210
340
1,020
280
60
325
177
70
210
475
35
167
20,000
* Based on future projections from February, 1979 data as estimated
in ref. [4].
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Next, using the ratio of methanol to ammonia production
determined above, the nationwide production capacity of methanol
from converted ammonia plants can be estimated for 1981. The
nationwide production for methanol is about 16.4 million tons per
year. The specific volume of methanol is about 7.2 barrels per
ton, so the annual volumetric production capacity would be 118
million barrels. On a calender day operating basis, the daily
production would be about 320,000 barrels. On an energy basis,
this is equivalent to a production of 150,000 barrels of fuel oil
equivalent per day (BFOE/D)(based on an energy value of 2.11
barrels of methanol per barrel of fuel oil equivalent).
IV. Cost
The total capital cost of this conversion will be estimated
in this section. To determine these costs, capital costs will be
determined first for each converted ammonia plant. The cost of
each plant depends upon the plant size. The 81 U.S. ammonia
plants vary from a production of 8,000 tons per year (or 22 tons
per day) to a production as large as one million tons per year (or
2,790 tons per day).[4] Rather than attempt to calculate the cost
plant by plant, a cost for an average plant size will be estimated
for convenience. A straight average of the 81 ammonia plants,
based on a nationwide production of 20 million tons per year,
would yield a plant size of about 250,000 tons per year, or about
700 tons of ammonia per day. If these were converted to methanol,
each methanol plant would have the capacity to produce about 550
tons of methanol per day. On an energy equivalent basis, this
would amount to 1,990 BFOE/D.
Now that the average size plant has been determined, the cost
of converting an average-sized ammonia plant to a methanol plant
must be estimated. In section II above, it was determined that
the addition of the following units would be necessary when con-
verting an ammonia plant to methanol production: a compression
unit, two cryogenic units, sulfur guard beds, and a methanol
synthesis unit. The cost for these additional units for
converting to this average size methanol production plant is shown
in Table 2. These costs were scaled to a production of 550 TPD
from plant sizes found in current studies,[5,6,7,8,9] ranging from
a production of 1800 TPD to 75,000 TPD methanol using a scaling
factor of 0.75. This is a common capital scaling factor for
chemical producing industries.[10] Table 2 shows the middle of
the range of these scaled costs. The sum of these costs is $22
million (1981 dollars) per plant. In addition, there are probably
other costs involved when converting from ammonia to methanol
production. Since these costs would be difficult to estimate, a
contingency factor of 20 percent will be allotted. Thus, the
capital cost for the conversion units with contingency is £26
million for a 550 TPD plant. Since there are approximately 81 of
these plants nationwide, the total cost to the nation would be
approximately $2.1 billion.
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Table 2
Cost of Methanol Producing Units
(Millions of First Quarter 1981 Dollars, 550 TPD)
Technology/Synthesis Cost*
Synthesis Gas Compression $ 1
Two Cryogenic Recovery Units $ 4
Sulfur Removal and Recovery/Methanol Drying $ 3
Methanol Synthesis $14
Total $22
* Costs are the middle of the range of costs found in current
literature,[4,5,6,7,8] and are scaled to a methanol production of
550 TPD (1900 BFOE/D), using a 0.75 capital scaling factor.
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The cost of converting an ammonia plant should be compared to
the cost of constructing a new natural gas based methanol plant to
observe the possible savings involved. According to a report by
ICF,[11] the cost of a new methanol plant using natural gas as
feedstock would be about $140 million (in 1981 dollars) for a
2,000 TPD plant. To accomplish an annual production of 16.4 mil-
lion tons per year (or the amount if all ammonia plants were
converted to methanol production), approximately 22 of these new
methanol plants would be required. The total cost of these plants
would be about $3.1 billion. This is approximately 50 percent
higher than the nationwide cost of $2.1 billion determined above
for converting the nation's ammonia plants to methanol production.
Thus, the cost of producing methanol from converted ammonia
plants is about $2.1 billion nationwide and appears to be roughly
one-third less expensive than building new methanol plants, which
cost about $3.1 billion. Of course, in the long run, final
justification of converting an ammonia plant to methanol produc-
tion as opposed to building new plants would not be based on the
simplified estimate of determining capital costs in each case.
Instead, an investigation is necessary to weigh the economics of
eliminating ammonia production and increasing methanol produc-
tion. Such an economic study, however, is beyond the scope of
this report. This report only shows that the capital costs for
producing a determined amount of methanol are reduced by approx-
imately one-third if ammonia plants are converted rather than if
new methanol plants were constructed.
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References
1. Buividas, L.J., "Coal to Ammonia: Its Status,"
Chemical Engineering Progress, May, 1981.
2. Shreve, Norris R. and Joseph A. Brink, Chemical Process
Industries, McGraw-Hill, Inc., 4th edition, 1977. ~"
3. Kirk, Othmer, Encyclopedia of Chemical Technology, Vol.
2, 3rd Ed.
4. "Brighter Days Ahead in Ammonia?" Farm Chemicals,
March, 1979.
5. Ralph M. Parsons, Co. for EPRI, "Screening Evaluation:
Synthetic Liquid Fuel Manufacture," EPRI AF-523, August, 1977.
6. C.F. Braun and Company for EPRI, "Coal to Methanol Via
New Processes Under Development: An Engineering and Economic
Evaluation," October, 1979. EPRI AF-1227.
7. DuPont Company, For U.S. ERDA, "Economic Feasibility
Study, Fuel Grade Methanol From Coal For Office of Commercial-
ization of the Energy Research and Development Administration,".
McGeorge, Arthur, 1976 TID-27606.
8. Badger Plants, Incorporated, "Conceptual Design of a
Coal-to-Methanol Commercial Plant," Vol. I-IV, for DOE, FE-2416-
24, February, 1978.
9. Exxon Research and Engineering Co., "Production
Economies for Hydrogen, Ammonia, and Methanol During the 1980-2000
Period," Cornell, H.G., Heinzelmann, F.J., and Nicholson, E.W.S.,
April, 1977.
10. Peters, Max S. and Timmerhaus, Klaus D., Plant Design
and Economics for Chemical Engineers, McGraw-Hill Company, Second
Edition, 1968.
11. "Methanol from Coal: Prospects and Performance as a
Fuel and as a Feedstock," Prepared for the National Alcohol Fuels
Commission by ICF, Incorporated, December, 1980.
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