Chemical Process
Industries [1]
LESSON 5:
COAL CHEMICALS
Contents
The destructive distillation of coal
Recovery of coal chemicals
Distillation of coal tar
Coal to chemicals
Introduction
Most chemicals from coal were initially obtained by destructive
distillation, furnishing chiefly aromatics
Aromatics obtained by processing petrochemicals: Benzene,
toluene, xylene, naphthalene, methylnaphthalenes
With advancing application of chemical conversion of coal, many
more chemicals can be made from coal (coal chemicals)
whenever economical
Coal chemicals (except metallurgical coke) are very competitive
Chemicals from coal
Introduction
Coal is a fundamental fuel, but petrochemicals now furnish most of
the basic raw materials for many essential industries
Dyes, medicines, pesticides, elastomers, modern plastics, etc.
Coal forms the world’s largest reserve of concentrated raw material
from which chemicals can be extracted and produced
It is also a cheap source of heat and power used for processing
Introduction
Production of gas and aromatics from coal have been curtailed by
petrochemical and natural gas competition
Research are directed to making new or old chemicals from coal,
lignite and shale through improved technology
Continuing investigations aim to eventually supply motor fuels and
other organic chemicals from coal at competitive prices
Destructive distillation of coal
Destructive distillation
a process by which organic substances such as wood, coal, and oil
shale are broken down by heat in the absence of air
causes the substances to break down into solids, liquids, and gases,
which are then used to make products such as coke, charcoal, oils, and
ammonia
When coal is thermally pyrolyzed or distilled by heating without
contact with air, it is converted into a variety of solid (coke and coal
tar), liquid (ammonical liquor) and gaseous products (coal gas)
Products from coal
Destructive distillation of coal
Nature and amount of coal product depends upon
Temperature in pyrolysis (500-1000°C, mostly maintained above 900°C)
Variety of coal
Coke - principal product by weight
Low-temperature carbonization – for process from 450 to 700°C
Small quantity of gaseous products, large quantity of liquid products
High-temperature carbonization – for process above 900°C
Larger yield of gaseous products than liquid products
Pyrolysis of Coal
(Step-by-step decomposition)
1. As the temperature is raised, the aliphatic carbon-carbon bonds
break first. Reaction begins below 200°C.
2. Carbon-hydrogen linkages break next or at near 600°C.
3. The elimination of heterocycle complexes and progressive
aromatization are the essential reactions taking place during the
decomposition as the carbonization proceeds.
4. The molecular weights of the intermediate products regularly
decrease as the temperature rises. Water, carbon monoxide,
hydrogen, methane, and other hydrocarbons are evolved.
5. Decomposition is at maximum between 600 and 800°C. All above
reactions vary markedly in their extent depending on the rate of
heating as well as the temperature attained.
Example of coke pyrolysis
Coal consists of large heterocyclic nuclei-monomers, with alkyl side
chains held together by 3-D C-C groups, and includes functional
oxygen groups
History of Coke
0ver 2,000 years ago
Coke was an article of commerce among the Chinese
Middle ages
Coke was used in the arts for domestic purposes
1620
First recorded production of coke in an oven
Middle of 19th century
Coal tar and coal-tar products were regarded as waste
History of Coke
1792
First successful experiment involving the production of gas from coal by
William Murdock
1812
Murdock’s gas lighted the streets of London
1856
Synthesis of the first coal-tar color (mauve) by Sir William Perkin
Coal tar became a commercial product
Laid the foundation of coal-tar-dye industry
1893
First battery of Semet-Solvay ovens was erected in New York
Uses and Economics
Coke is the product of largest tonnage from coal distillation
Demand for coke depends on demand for steel*
98% of coal-tar production is from by-product ovens
The liquid products (coal-tar & ammonia liquor) are not so large in
volume, but important in chemical-recovery ovens
Uses of coal tar: fuel, roofing, roads
Aromatics from petroleum and coal tar are made into:
Dyes, intermediates, medicinals, flavors, perfumes, resins, rubber
chemicals, etc
Data on crude
aromatics from
coal and
petroleum
Coking of Coal
Two main types of coking procedures for coal:
The Beehive (obsolete/primitive method) and the By-product
By-product coking
Carefully blended coal charge is oven-heated on both sides so that the
heat travels toward the center, and thus produces shorter and more
solid pieces of coke (compared to Beehive method)
Air is excluded so that no burning takes place within the oven (heat
supply completely from flues on the sides)
40% of oven gas (after stripped of by-products) is returned and burned
for the underfiring of oven battery (some used for local fuel gas)
Coking of Coal
By-product Coking
Recovery of Coal Chemicals
Low-temperature Carbonization
By-product Coking
By-product coke oven:
Narrow chamber (11 to 12 m long, 4 m high, 0.4 to 0.6 m wide at one
end, 0.35 to 0.4 m wide at the other end)
Holds 15 to 25 t of coal
Used for carbonizing coal only in large amounts
Built in batteries of 10 to 100 ovens
The oven block is built of refractory brick, with heating flues between the
coking ovens (Fig. 5.4)
(~17 h)
By-product Coke-oven Procedure
1. Coal is transferred, crushed and screened
2. Coal is charged to a hot, empty oven
3. Coal is chemically transformed to coke and volatiles by pyrolysis
4. Hot coke is pushed out of the oven, quenched and transported
5. Condensable products of distillation are liquefied and collected in the
hydraulic main
6. Foul gas is cooled, and tar extracted
7. Ammonia is removed from gas as ammonium sulfate
8. Gas is cooled and subjected to benzene and toluene removal by
absorption in straw oil
9. Hydrogen sulfide is removed
10. Purified gas is metered and transferred to consumers
Products of Coal-tar Distillation
Product Boiling Point, °C
Side stream 1 Light oil to 170
Side stream 2 Carbolic oil 170 – 205
Side stream 3 Naphthalene oil 205 – 240
Side stream 4 Creosote or wash oil 240 – 280
Residue 5 Residue of anthracene 270 – 340
Pitch 6 Residuum or pitch 325 – 400
The Wilton principle of recirculation of hot pitch at 350°C, mixed with
crude tar at 120°C, raises the temperature of the pitch-tar leaving
the pipe still to only 350°C and avoids thermal cracking and
vaporization of the pipe still.
Koppers-
Becker Oven
Regenerative type with
individual heat regenerators,
generally from side to side,
underneath the oven
Gas burns upward, crosses
over the top of the oven,
comes downward on the
other side, exits through the
regenerator oven underneath
Reversal of the air and waste
gas flow is made from side to
side every half hour
Continuous Coking Processes
Coke and char can be made by continuous processes (ex. Lurgi-
Spulgas retort), but the liquid products and coke formed vary
greatly from the products obtained by a by-product oven
Low-temperature carbonization once looked promising as a method
of producing fuel gas and reactive char, which is useful as a
smokeless fuel for domestic heating
High-temperature continuous carbonizers are usually operated to
produce synthesis gas with low yields of coke.
Recovery of Coal Chemicals
The gaseous mixture leaving the oven is made up of permanent
gases that form the final purified coke-oven coal gas for fuel, along
with condensable water vapor, tar, and light oils, and solid particles
of coal dust, heavy hydrocarbons, and complex carbon
compounds
Significant products recoverable from the vapors:*
Benzene, toluene, xylenes, creosote oils, cresols, cresylic acid,
naphthalene, phenols, xylols, pyridine, quinoline, and medium and hard
pitches (usable for electrode binders, road tar, or roofing pitch)
t
The Phosam Process
another process for ammonia removal from coke oven gas
NH4H2PO4 absorbs ammonia to form more alkaline phosphates such
as (NH4)2HPO4 and (NH4)3PO4, which are returned to the original
form by steaming, thus releasing the ammonia.
In a typical absorption cycle, lean 40% phosphate solution (the
molar ratio of NH3/H3PO4 is less than 1.5) soaks up all but traces of
NH3.
The rich ammonium phosphate solution is reboiled in a distillation
tower in which NH3 vapor and a lean phosphate solution are
separated for reuse.
Low-temperature Carbonization
Coal is carbonized at 400 to 600°C with the main object of
obtaining maximum yields of liquid products and producing
semicokes (chars) containing 8 to 20% volatile matter.
Characteristics and yields of the various products depend upon the
coal, the temperature, and the treatment.
Distillation of Coal Tar
Coal tar is a mixture of many chemical compounds, mostly
aromatic, which vary widely in composition
It is a by-product of the destructive distillation or pyrolysis of coal
Most of the tar [in the US] is produced as a by-product of the
manufacture of blast-furnace coke.
The quality and quantity of tar from this operation vary depending
on the rate of production of the ovens and the nature of the coal
used.
The specific gravity vary from 1.15 to 1.2, and the quantity of tar vary
from 30 to 45 L per metric ton of coal.
Fractionating
Column
In a modern refinery equipped with a
fractionating column for the primary
distillation, products must usually be sharp
fractionated, with a minimum of
overlapping.
Process must be thermally economical, and
the furnace so designed and constructed
that repairs and fuel usage are at a
minimum.
No one product exceeds 0.5% of the crude.
Distillation of Coal Tar
Methods of Distillation
Miscellaneous Uses of Coal Tar
Fractionation and Purification of Coal Tar Chemicals
Methods of Distillation
1. The 10,000- to 30,000-L batch still (obsolete, but a few are still being
operated), which has been much improved and used for special
end products such as pipe enamel
2. The continuous still, with a single distillation column, using side
streams
3. The continuous unit, using multiple columns with reboilers
(recirculation of the residue improves the operation)
Products of Distillation
1. Light oils usually comprise the cut up to 200°C.
They are first crudely fractionated and
agitated at a low temperature with the
concentrated sulfuric acid, neutralized with
caustic soda, and redistilled, furnishing
benzene, toluene, and homologs.
2. Middle oils, or creosote oils, generally are the 3. Heavy oil may represent the
fraction from 200 to 250°C, which contain fraction from 250 to 300°C, or it
naphthalene, phenol, and cresols. The may be split between the middle
naphthalene settles out on cooling, is oil and the anthracene oil.
separated by centrifuging, and is purified by 4. Anthracene oil is usually the
sublimation. After the naphthalene is fraction from 300 to 350°C. It is
removed, phenol and other tar acids are washed with various solvents to
obtained by extraction with 10% caustic soda remove phenanthrene and
solution and neutralization, or "springing" by carbazole; the remaining solid is
carbon dioxide These are fractionally distilled. anthracene.
Miscellaneous Uses of Coal Tar
A substantial fraction of the coal tar produced continues to be used
as fuel.
Coal tar is also utilized for roads and roofs.
For these purposes, the tar is distilled up to the point where thermal
decomposition starts.
This “base tar” is then oiled back (diluted) with creosote oil to ensure
satisfactory rapid drying.
Similar tars are used to impregnate felt and paper for waterproofing
materials.
Fractionation and Purification of
Coal Tar Chemicals
Largely because of the present competition from aromatic
chemicals produced from petroleum, interest in aromatics from coal
has temporarily decreased.
At one time coal tar was the sole source of pyridine; however
synthetic processes using aldehyde and ammonia are now
supplying the increased demand. This is also true of phenol.
In Europe, which has much coal and little petroleum, there is
continued interest in coal chemicals.
Solid chemicals that
could be obtained
from coal tar
The product of largest
potential is phenanthrene (the
second most abundant
material in coal tar), of which
250,000 t can be recovered in
the western world yearly as
soon as profitable uses can be
found.
Anthraquinone is the basis of
many vat dyes, but it is
cheaper to synthesize it from
phthalic anhydride than to
oxidize anthracene.
Coal to Chemicals
Coal to Chemicals
Hydrogenolysis (Hydrogenation-Pyrolysis)
Coal Research
Hydrogenolysis
Coal Research
end
