The Production of Chemicals from Coal

Coal has been considered a major component of U.S. energy reserves for a long time, and more recently it
has become an important raw material for the production of chemicals. The worldwide abundance of coal,
as reflected in Table 1, and its proximity to sites where it can be used, have made it an attractive alternative
to more costly or less strategically located feedstocks. Most approaches to the conversion of coal to
chemicals involve either coal gasification or coal liquefaction, processes that convert solid coal to fluids.
The fluids are more easily handled and processed than the original coal; they can be used as fuels site or
after pipeline transmission, or they can be converted to chemical intermediates. A secondary but important
aspect of these conversion processes is that potentially harmful materials in coal are more easily separated
from the fluids produced by gasification or liquefaction than from either the solid coal or the off-gases from
its combustion.
The most common coal gasification process involves the reaction of carbon, the primary constituent of
coal, with steam to produce carbon monoxide and hydrogen.
C + O2

CO + H 2

(1)

The carbon monoxide and hydrogen can be separated from the other compounds exiting the gasifier and
used
either as a fuel or a feedstock to a chemical manufacturing process. Simultaneously, oxygen fed to the
reactor along with steam reacts with carbon to form carbon dioxide.
C + O2

CO 2

(2)

In addition, there is significant reaction between water and carbon monoxide in the gasifier via the watergas
shift reaction.
CO + H2O

CO2 + H2

(3)

Although Reactions 1, 2 and 3 are the primary reactions in coal gasification, there are important secondary
reactions. For example, the hydrogen-rich atmosphere in the gasification reactor causes the formation of
hydrogen sulfide from the sulfur usually found in coal and of small amounts of methane.
S + H2

H 2S

(4)

C + 2H 2

CH 4

(5)

Table 1: Distribution of Proven Coal Reserves In Billions of Tons

Country
Soviet Union
United States
Peoples Republic of China
German Federal Republic
Australia
India
Republic of South Africa
Others

Reserves
273
182
101
40
24
12
11
55
698

From R. F. Probstein and R. E. Hicks, Synthetic Fuels, McGraw-Hill, NewYork, 1982.

Various hydrocarbon feedstocks other than coal can be used for production of chemicals, including crude
oil, natural gas, and wood. Each of these raw materials yields a synthesis gas containing carbon monoxide
and hydrogen, much as described above. As the hydrogen-to-carbon ratio in the synthesis gas differs from
one feedstock to another, the differences may be used in selecting a feedstock to produce a specific product.
For example, natural gas reforming yields a synthesis gas with a high hydrogen content that can be used as
a raw material for manufacturing hydrogen-rich products such as ammonia. Gasification of coal, on the
other hand, provides a gas with a high carbon monoxide content that can be used as a raw material for
producing species with lower hydrogen contents such as acetic anhydride(C4H6O3). The most efficient use
of raw material is generally achieved when a feedstock contains hydrogen and carbon monoxide in roughly
the proportions required to form the desired chemical product. Of course, there are other factors to consider
in choosing a feedstock, such as the projected stability in price and supply of the feedstock and the location
of the feedstock in relation to the plant.
Your company has plans to build a plant to convert coal to acetic anhydride, a chemical vital to the
companys product line. The plant is to produce 160,000 metric tons of acetic anhydride per year. It is
anticipated that the completed process will operate continuously 350 days/ yr. The composition of coal
from the nearest deposit is given in Table 2. Judging from the sulfur content, production of significant
quantities of H2S is expected. Since H2S poisons (deactivates) catalysts used in the conversion of hydrogen
and carbon monoxide into acetic anhydride, it must be removed from the gas leaving the gasifier. It is your
responsibility to assist with the setting of design variables necessary for sizing equipment.

Table 2: Composition of Coal to be Used as Feed to the Gasifier

Element
Weight Percent

C
52.5

O
H
18.3 4.8

S
N
Ash
0.6 1.2 22.6

The coal contains 10.5% moisture. The hydrogen and oxygen percentages given here include the masses
of these elements in the coal moisture.

PROCESS DESCRIPTION
Before it can be fed to the gasification reactor, coal must be ground to meet specifications on particle size.
The grinding is accompanied by the generation of coal dust that can represent a loss of raw material and a
hazard to both personnel and equipment. This problem is minimized by recognizing that one of the primary
reactions in coal gasification is between coal and water, and that grinding and separating the resulting coal
particles by size can be performed on a coal-water mixture as well as on dry coal. The ratio of dry coal to
water in the feed to the gasifier is to be 2 kg coal/kg water, and this ratio is set with the water added to the
grinding and classification operations.
The reactor in which gasification is to be carried out is an entrained flow gasifier. A coal-water slurry is fed
to the gasifier along with high-pressure oxygen. Both feed streams may be assumed to be at 25C. The
reactor is operated adiabatically at 6300 kPa absolute.
At these conditions, only trace quantities of hydrocarbon byproducts other than methane are present in the
gas leaving the gasifier, and essentially all of the reactive carbon, hydrogen, and sulfur in the coal are
reacted. The gas and molten ash (slag) leaving the gasifier are fed to a wash tank where the gas is bubbled
through water and the slag is solidified. The gas leaving the wash tank is fed to a scrubber where it contacts
a water spray. Small amounts of residual particulate matter are removed from the gas, which is also cooled
from 220C to 170C. The water with which the gas is contacted has been pumped from the wash tank,
through a heat exchanger, and into the scrubber. The gas-liquid mixture formed in the scrubber is separated
into saturated gas and liquid streams at 170C and 5960 kPa absolute, and the water is returned to the wash
tank. Solids collected in the wash tank are allowed to settle, and are then removed along with the water
condensed from the gas leaving the gasifier. The composition of the gas leaving the gasifier is given in
Table
3.
The ratio of hydrogen to carbon monoxide in the gas leaving the scrubber must be adjusted to satisfy
stoichiometric requirements associated with downstream reactions. The adjustment is made by contacting a
portion of the gas leaving the scrubber with a catalyst that increases the rate at which the water-gas shift
reaction occurs. The shift reactor consists of a fixed bed of cobalt-molybdenum catalyst pellets and operates
at 300C and 5615 kPa absolute.

The product from the water-gas shift reactor and the unreacted portion of the synthesis gas stream obtained
from the gasifier are blended and cooled by generating steam in waste-heat boilers. Water is removed
completely from the cooled gas in a molecular sieve drier. The dry gas is then fed to an acid gas removal
system where all of the containing compounds are separated and sent to a sulfur recovery reactor, and
99.9% of the CO2 is separated and either vented or recovered for use elsewhere in the plant.
The acid gas removal system consists of two absorption columns, both of which operate at 5000 kPa
absolute, and a solvent regeneration section. The gas enters the first absorption column and contacts
refrigerated methyl alcohol flowing countercurrently to the gas. In the column, some CO2 and essentially
all of the H2S are absorbed in the methyl alcohol. The gas leaving this column is sent to a second
absorption column where most of the remaining CO2 is absorbed in additional methyl alcohol. The gas
exiting the second column is at -30C and contains 0.1% of the CO2 that entered the first absorber with the
crude coal gas.
There are two separate operations in the regeneration section of the acid gas removal system. In the first,
the methyl alcohol from the first absorber is flashed (abruptly exposed to a lower pressure, causing a
significant fraction of the absorbed gases to come out of solution). Essentially all of the absorbed CO2
and H2S are recovered in the off-gas, and the regenerated methyl alcohol is recirculated to the first
absorber. The off-gas from the flash tank is a mixture consisting of 15 mole% H2S and 85 mole% CO2. In
the second operation, methyl alcohol from the second absorber is fed to a stripping column where it flows
downward to a reboiler. Indirect steam heating (heat transferred through a heat transfer surface) is used to
vaporize a portion of the methyl alcohol, which is returned to the column and strips the CO2 from the
liquid methyl alcohol. The regenerated liquid methyl alcohol is cooled and recirculated to the second
absorber.
Sulfur emissions are potential health hazards, and safe disposal of the H2S separated from the product gas is
an important provision of the proposed plant. To accomplish this, the hydrogen sulfide is converted into
elemental sulfur in a Claus process. In this process, the H2S rich gas discharged from the flash tank is split,
with one-third going to a furnace where the hydrogen sulfide is burned at 1 atm with a stoichiometric
amount of air to form SO2.
H2S + 1.5 O2

SO2 + H2O

(6)

The hot gases leave the furnace and are cooled prior to being mixed with the remainder of gas from the
flash
tank. The mixed gas is then fed to a catalytic reactor where hydrogen sulfide and SO2 react to form
elemental
sulfur.
2H2S + SO2

2H20 + 3S

(7)

The gases leave the reactor at 380C and are cooled to 130C by generating steam at 205kPa from saturated
liquid at 205kPa. Liquid sulfur is condensed and recovered as the hot gases are cooled at atmospheric
pressure.

As an intermediate step in the production of acetic anhydride, carbon monoxide and carbon dioxide are
reacted with hydrogen to produce methanol.
CO + 2H2
CO 2 + 3H 2

CH3OH
CH3OH + H2O

(8)
(9)

These reactions are carried out at 200C and 4925 kPa absolute. The feed to the methanol reactor is formed
by combining recycle from the reactor with a fresh feed stream containing 5% excess hydrogen, based on
complete conversion of CO and CO2 to methanol. The composition of the gas leaving the acid gas
removal system is adjusted to meet the fresh feed requirement on excess hydrogen. This is
accomplished by splitting the gas from the second absorption column into two streams, one of which is
sent to a low-temperature separation unit while the second is blended with the hydrogen-rich stream
exiting this unit. The separation is designed to condense 95% of the inlet carbon monoxide and to
operate at 5000 kPa.

Table 3: Dry-Basis Composition of Syngas Exiting Gasifier

Component CO
H2
CO2 N2 CH4 H2S
mole%
47.95 37.25 13.85 0.6 0.1 0.25
Reactions 8 and 9 do not go to completion, and conversions of CO and CO2 must be estimated based on
equilibrium constants available from the literature. The equilibrium constant K8 for Reaction 8 is given here
in terms of the partial pressures of reactants and products in kPa and system temperature in degrees Kelvin
K8 = pM/pC O p2H =
(10)
-4
-3
-8
1.390 x 10 exp(21.225+ (9143.6/T) 7.492 ln T + 4.076 x 10 T 7.161 x 10 )
where the subscripts M and H represent methanol and H2 respectively. Note that Reaction 9 can be
represented as the sum of Reaction 8 and the reverse of the water-gas shift reaction.
H2 + CO2

CO + H2O

(11)

The equilibrium constant for Reaction 11 is given by the equation

K11 = (pCOpW)/(pCO2pH) =
3.330 exp(13.148 (5639.5/T) 1.077 ln T 5.44 x 10-4T + 1.125 x 10-7T2 +
(49170/T2))

(12)

Where the subscript W represents water. The stream leaving the reactor is sent to a unit process that
separates methanol and water from the noncondensables, and then separates the methanol and water. The
stream of noncondensables, which consists of carbon dioxide, carbon monoxide, hydrogen, methane, and
nitrogen, is

sent to a multiple-unit process that removes all of the nitrogen and methane and some of the hydrogen. The
gas that remains contains the quantity of hydrogen stoichiometrically required to convert all of the CO and
CO2 to methanol. This stream is recycled to join the fresh feed to the reactor.
Finally, acetic anhydride is produced in two successive reactions. Methyl acetate is first synthesized by
reacting the methanol with acetic acid obtained from another manufacturing unit.
CH 3 OH + CH 3 COOH

CH 3 COOCH 3 + H 2 O

(13)

The feed to the reactor contains methanol and acetic acid in stoichiometric proportion. Chemical
equilibrium
is achieved in the reactor. At the reaction conditions, the equilibrium constant K13 in the following
relationship is 5.2:

K13 = xMA xW/ xM xA

Where xi is the mole fraction of i in the product solution, and the subscripts MA and A represent methyl
acetate and acetic acid respectively. The product from the reactor is sent to a facility that separates the
reactants from the products and methyl acetate from water. The reactants are recycled to the reactor. The
methyl acetate and carbon monoxide from the low temperature separation unit are fed to a second reactor in
stoichiometric proportion, and the two substances react completely to form acetic anhydride.
CH 3 COOCH 3 + CO

CH 3 COOCOCH 3

(15)

PROBLEMS
In solving the problems that follow, cite all sources of data not given in the process description and clearly
state all assumptions.
1. Construct a detailed flowchart of the process, showing known compositions, flow rates, pressures,
and temperatures. Use this chart to keep track of your calculations and as a basis for a final
flowchart to be prepared when you have finished the case study.
2. Assume there are no side reactions in the synthesis of methanol, methyl acetate, and acetic
anhydride, and calculate the molar flow rates of reactants (kmol/h) in the fresh feeds to each of the
reactors. Where fresh feed must be supplied from a source external to the process, calculate the
feed rates of these materials in kg/h.
3. Estimate the amount of oxygen fed to the gasification reactor in kmol and standard cubic meters
per kg of coal fed to the process.
4. Suppose that air, rather than pure oxygen, were fed to the reactor. What would be the flow of air in
3

kmol and standard m per kg of coal fed to the process? What would be the composition of the gas
leaving the gasifier under these conditions? Suggest reasons based on these calculations for the use
of O2 instead of air.

5. If all of the sulfur in the coal reacts to form H2S, determine the air requirements for the Claus plant
3
in kmol and standard m per kg of coal fed to the process.
6. Estimate the mole fraction of water in the gas exiting the scrubber. What is the rate (kg/kg coal) at
which water exits the scrubber in the product gas?
7. Determine the fraction of the gas leaving the scrubber that must be sent to the water gas shift reactor.
Calculate the composition of the stream resulting from mixing the product from the water-gas shift
reactor and the stream bypassing the reactor.
8. Determine the coal feed rate (kg/h), and calculate the rates at which oxygen is fed to the gasifier
(kmol/h) and air is fed to the Claus plant (kmol/h).
9. Estimate the composition of the product gas leaving the acid gas removal system. What fraction of
this gas is sent to the cryogenic separator? What is the composition of the gas resulting from
blending the H2-rich product from the cryogenic separator with the stream bypassing the separator?
10. Using the equilibrium constants for Reactions 8 and 11, determine the composition of the effluent
from the methanol synthesis reactor. What is the single-pass conversion of carbon monoxide? (A
trial-and-error solution is required.)
11. Based on the equilibrium constant given for Reaction 13, calculate the composition of the product
stream leaving the methyl acetate synthesis reactor and the single-pass conversion of methanol to
methyl acetate. Determine the recycle rates of methanol and acetic acid.
12. Propose a modification of the methyl acetate reactor that would involve recycle of primarily one
reactant. (Hint: Consider the effect of feeding an excess of one of the reactants on product
composition.) Estimate the recycle rate for the proposed modification. Summarize features of this
mode of operation that could make it more economical than the mode requiring recycle of both
reactants.
13. What fraction of the elemental sulfur leaving the Claus plant reactor is condensed? (The
dependence of the vapor pressure of sulfur on temperature is given in Table 3-7 of Perrys
Chemical Engineers Handbook.) A suggestion has been made to burn the residual sulfur in the
gas stream exiting the sulfur condenser, forming SO2 and discharging this material into the
atmosphere. Estimate the emission rate of SO2 (kg/h) if this suggestion is followed.
14. The plant has a methanol storage tank with a capacity of 2,000,000 liters. The average temperature
0
of the liquid in the tank is 40 C and the tank is padded with nitrogen at a pressure of 1 atm
(absolute) to reduce explosion hazards. The vapor space in the tank can be assumed saturated with
methanol. The volume of methanol stored in the tank increases from 800,000 to 1,200,000 liters
twice a day, and in the process a portion of the vapor space is displaced by liquid methanol. What
would be the methanol vapor emission to the atmosphere (kg/day) if there were no emission
control devices? Propose two different schemes to reduce vapor emissions.
15. Determine the relationship between flow rate and temperature of the water fed to the scrubber. Is
the rate at which heat must be removed from the water as it is pumped from the wash tank to
the scrubber affected by the flow rate of water? Explain.
16. Assume that the temperature of the gases and slag leaving the gasifier is 1100C. Estimate the total
rate at which heat must be removed from the wash tank-scrubber system. (Note: The actual
temperature of such streams in commercial entrained-flow gasifiers is closer to 1350C.) The

following properties of ash and slag may be used: for ash, Cp(kJ/kg C ) = 0.604 + 0.586 x 10
-3
Hm= 710 kJ/kg; for slag, Cp(kJ/kg C ) = 0.767 + 0.744 x 10 T(K),
17. The portion of the gas from the scrubber that is not sent to the water-gas shift reactor and the
product gas from the water-gas shift reactor are used to generate steam in waste-heat boilers.
Steam can be generated and used at three absolute pressures 2858 kPa, 790 kPa and 205 kPa.
The relative worths of steam at these pressures are 1.3, 1.2 and 1.0. Given that the gas fed to the
acid gas removal system must be cooled to 100C and that gas fed to a boiler can be cooled to
within 5C of the temperature of the steam it generates, propose a bank of waste-heat boilers that
maximizes the value of the generated steam, How much of each steam is generated in the optimum
configuration? Why do the respective steams have different values?
18. How much low-pressure steam (205kPa) in kg/h can be generated by heat recovered the Claus
plant?