LIQUEFACTION

TUTUK DJOKO KUSWORO

DEPARTEMENT OF CHEMICAL ENGINEERING

FACULTY OF ENGINEERING DIPONEGORO UNIVERSITY
SEMARANG
 PROSES PENCAIRAN BATUBARA

LATAR BELAKANG:
KONVERSI BBM KE BBG hal ini karena BBM yang semakin
menipis
Harga Gas yang murah daripada BBM
Cadangan Gas lebih besar daripada BBM
Kendala Konverter kit, baru ada sekitar 250.000
Jumlah kendaraan terlalu banyak
Apakah bisa berjalan BBM--- BBG????????
Alternatif membuat bahan bakar cair
 Introduction

Liquefaction is the conversion of coals into liquid

products.
The three methods by which liquids can be derived from
coals are :
1. pyrolysis,
2. indirect liquefaction, and
3. direct liquefaction.
 Introduction

In pyrolysis processes, the liquids are a by-product of

coke production.
The term liquefaction refers to the conversion of the coal
to a product that is primarily a liquid.
In indirect liquefaction, the coal is gasied into a
mixture of carbon monoxide and hydrogen (i.e., syngas).
The syngas is then processed into liquid products using
FischerTropsch synthesis.
 Introduction

In direct liquefaction, also referred to as coal

hydrogenation, coal is mixed with a hydrogen-donor
solvent and reacted with hydrogen or syngas under
elevated pressures and temperatures to produce a liquid
fuel.
Indirect liquefaction is used quite extensively through out
the world, while direct liquefaction has not be enable to
compete with other liquid or gaseous fuels.
Introduction
 Reforming

Steam Refoming

Partial Oxidation

Auto thermal Reforming


Direct Vs Indirect Liquefaction
DIRECT
LIQUEFACTION
Adds hydrogen to break down
the coal
Dissolves in a solvent followed
by hydrocracking
Operates at 450 C and 170 bars
Light products are distilled
Medium and heavy distillates
obtained from vacuum distillation
Liquid yields of 70% of the dry
weight of coal feed
Further upgrade is needed for
use as transportation fuels
8
INDIRECT
LIQUEFACTION
Complete breakdown of coal
with steam and oxygen
Sulfur is removed from the
syngas
Syngas reacted over catalyst at
300 C and 20 bars
Produces a lighter suite of
products; high quality gasoline
and petrochemicals
Oxygenated chemicals
Fuel H/C ratio
 Brief History of Coal Liquefaction

Coal was hydrogenated in the laboratory by Berthelot as early as

1869. The reaction was carried out with hydriodic acid at 520F for 24
hours, and a 67% yield of oil containing aromatics and naphthenes
was obtained.
In the early 1900s, German scientists and engineers invented and
developed two processes that enabled them to produce synthetic
petroleum from their coal supplies and to establish the worlds first
technologically successful synthetic liquid fuel industry.
In 1911, Friedrich Bergius obtained oil by hydrogenating coal
without a catalyst under hydrogen pressure at 570 to 660F.
At the end of 1925, I.G. Farben, a chemical company, hydrogenated
coal using a molybdenum oxide catalyst. The presence of the
catalyst allowed the hydrogenation of coal in the presence of excess
hydrogen at low pressure and at temperatures of 750 to 840F.
 Brief History of Coal Liquefaction

In 1920, Franz Fischer and Hans Tropsch at the KaiserWilhelm

Institute for Coal Research in Mlheim, invented a second process
for the synthesis of liquid fuel from coal.
By the mid-1930s, I.G. Farben and Ruhrchemie had started to
industrialize synthetic liquid fuel production, resulting in the
construction of 12 coal hydrogenation and 9 FischerTropsch plants
by the time World War II ended.
South Africa, fearing boycott as a result of their racial policies,
decided to proceed with a synthetic fuels plant in 1951,
 Pyrolysis

High-temperature carbonization is the oldest route for the production

of liquids from coal, wherein hydrocarbon liquid is predominantly a
byproduct of coke-making.
The low yields (<~5%) of liquid product and relatively high upgrading
costs mean that traditional high-temperature carbonization is not an
option for the production of liquid fuels on a commercial basis.
Mild pyrolysis is also a carbonization technology but with less severe
operating conditions. Mild pyrolysis consists of heating the coal to a
temperature in the range ~450-650C, driving off volatile matter from
the original coal and generating other volatile organic compounds
formed by thermal decomposition during the treatment.
Liquid yields are higher than for high-temperature carbonization, but
are still no more than 15-20% at most with the main product is chart.
 Pyrolysis

A higher yield of liquids can be obtained by rapid pyrolysis. These

processes operate at temperatures up to 1200C, but the residence
time of the coal is significantly reduced, to a few seconds at most.
Rapid pyrolysis is aimed at producing chemical feedstocks rather
than liquid fuels and process economics are likely to be highly
unfavorable for production of liquid fuels. There also appear to be
unresolved engineering difficulties.
The latest technology in USA is the Liquids from Coal (LFC) process.
It has been in commercial-scale operation since 1992.
The LFC process is a mild pyrolysis method for upgrading coal and
was developed by SGI International. There are two saleable
products: a low-sulphur, high heating-value solid known as process-
derived fuel (PDF) and a hydrocarbon liquid known as coal-derived
liquid (CDL). PDF yields are considerably higher than CDL yields.
 Pyrolysis

The coal is crushed and screened and then heated by a hot

gas stream on a rotary grate dryer.
The dried coal is then fed into the main rotary grate pyrolyser
where it is heated to ~540C by a hot recycled gas stream.
On discharge from the pyrolyser the solids are cooled and
pass to a deactivation step, consisting of treatment in a
vibrating fluidized bed with a gas stream of controlled oxygen
content.
The gas stream leaving the pyrolyser is cooled in a quench
tower, condensing CDL but leaving water in the gas phase.
Most of the residual gas is recycled to the pyrolyser, some
being burned in the pyrolyser combustor to provide the
necessary heat.
 Pyrolysis

The remaining gas is burned in the dryer combustor and

passes into the dryer gas recycle loop.
The purge from this loop is wet-scrubbed to remove
particulates and sulphur oxides. Purge liquor from the
scrubbers is discharged to ponds for evaporation.
After being stabilized by mild oxidation, the PDF, a low-
sulphur reactive fuel suitable for pulverized coal-fired
boilers, is shipped by rail to power plant. CDL is shipped
by rail to a fuel oil distributor.
Pyrolysis
 Indirect Coal Liquefaction

Indirect coal liquefaction differs fundamentally from direct

coal liquefaction in that the coal is first converted to a
synthesis gas (a mixture of H2 and CO) which is then
converted over a catalyst to the final product.
The synthesis gas is produced in a gasifier, where the
coal is partially combusted at high temperature and
moderate pressure with a mixture of oxygen and steam.
In addition to H2 and CO, the raw synthesis gas contains
other constituents (such as CO2, H2S, NH3, N2, and CH4),
as well as particulates.
 Indirect Coal Liquefaction

Before being fed to the synthesis reactor, the synthesis gas

must first be cooled and then passed through particulate
removal equipment.
Following this, depending on the catalyst being used, it may be
necessary to adjust the H2/CO ratio.
Modern high-efficiency gasifiers typically produce a ratio
between 0.45 and 0.7, which is lower than stoichiometric for
the synthesis reaction.
Some catalysts, particularly iron catalysts, possess water gas
shift conversion activity and permit operation with a low H2/CO
ratio.
Other catalysts possess little shift activity, however, and
require a ratio adjustment before the synthesis reactor.
 Indirect Coal Liquefaction

After shift conversion, acid gases (CO2 and H2S) are

scrubbed from the synthesis gas.
A guard chamber is sometimes used to remove the last traces
of H2S.
The cleaned gas is sent to the synthesis reactor, where it is
converted at moderate temperature and pressure, typically
498 to 613 K (435 to 645F) and 1.52 to 6.08 MPa (220 to
880 psia).
Products from the process depend on operating conditions
and the catalyst employed, as well as reactor design.
Typical products include hydrocarbons (mainly straight
chain paraffins from methane through n-C50 and higher),
oxygenates (methanol, higher alcohols, ethers), and other
chemicals (olefins).
Indirect Coal Liquefaction
Indirect Coal Liquefaction
 Fischer-Tropsch Synthesis

The best-known technology for producing hydrocarbons

from synthesis gas is the Fischer-Tropsch synthesis.
This technology was first demonstrated in Germany in
1902 by Sabatier and Senderens when they
hydrogenated carbon monoxide (CO) to methane,
using a nickel catalyst.
In 1926 Fischer and Tropsch were awarded a patent for
the discovery of a catalytic technique to convert
synthesis gas to liquid hydrocarbons similar to
petroleum.
 Fischer-Tropsch Synthesis

Other reactions may also occur during the Fischer-Tropsch

synthesis, depending on the catalyst employed and the
conditions used:
Fischer-Tropsch Synthesis
Reactor type
 Fischer-Tropsch Synthesis

The Synthol reactor developed by SASOL is typical of high-

temperature operation.
Using an iron-based catalyst, this process produces a very
good gasoline product having high olefinicity and a low
boiling range.
The olefin fraction can readily be oligomerized to produce
diesel fuel.
Low-temperature operation, typically in fixed-bed reactors,
produces a much more paraffinic and straight-chain
product.
Selectivity can be tailored to give the desired chain growth
parameter.
The primary diesel fraction, as well as the diesel-range product
from hydrocracking of the wax, is an excellent diesel fuel.
Fischer-Tropsch Synthesis
SASOL
 Oxygenated Chemicals

A whole host of oxygenated products, i.e., fuels, fuel

additives, and chemicals, can be produced from synthesis gas.
These include such products as methanol, isobutanol,
dimethyl ether, dimethyl carbonate, and many other
hydrocarbons and oxyhydrocarbons.
Typical oxygenate-producing reactions are:

Reaction (27-37) can occur in parallel with the methanol

reactions, thereby overcoming the equilibrium limitation on
methanol formation.
 Oxygenated Chemicals

The production of methyl acetate from synthesis gas is

currently being practiced commercially.
Following methanol synthesis, as shown by Reaction (27-
35), the reactions are:

Acrylates and methacrylates, which are critical to the

production of polyesters, plastics, latexes, and synthetic
lubricants, can also be produced from these oxygenated
intermediates.
DIRECT COAL LIQUEFACTION
 Introduction

Direct liquefaction transforms coal into liquid

hydrocarbons by directly adding hydrogen to the coal.
All direct-liquefaction processes consist of three basic
steps:
1. Coal slurrying in a vehicle solvent,
2. Coal dissolution under high pressure and temperature, and
3. Transfer of hydrogen to the dissolved coal.
However, the specific reaction pathways and associated
kinetics are not known in detail.
Introduction
 Bergius/I.G. Farben Process

The Bergius process was put in to commercial practice

by I.G. Farben in Leuna, Germany, in 1927, and
additional plants were erected in the 1930s.
The process operated in two stages.
1. Liquid-phase hydrogenation rst transformed the coal into
middle oils, with boiling points between 300 and 615F,
2. vapor-phase hydrogenation then converted these oils to
gasoline, diesel fuel, and other relatively light hydrocarbons.
 Bergius/I.G. Farben Process

The Bergius process converts 1 short ton of coal to 40-45

gallons of gasoline, 50 gallons of diesel fuel, and 35 gallons of
fuel oil.
The gasoline fraction contains 75 to 80% parafns and olens
and 20 to 25% aromatic compounds.
Liquid-phase hydrogenation of low-rank coals was usually
accomplished at 890 to 905F under pressures of 250 to 300
atm using an iron-oxide hydrogenation catalyst.
For liquid-phase hydrogenation of bituminous coals,
temperatures were similar, but pressures were in the range of
350 to 700 atm.
 Solvent Rening Processes

The solvent-rened coal (SRC) process is considered the

least complex of the various process schemes.
Hydrogenation of the coal in the SRC process occurs
at elevated temperatures and pressures in the
presence of hydrogen.
 SRC-I Process

In the SRC-I process, ground and dried coal is fed to the

react or as a slurry.
The transport liquid, or process solvent, is a distillate
fraction recovered from the coal hydrogenation product
and serves as the hydrogen donor.
The coal slurry and hydrogen are introduced into a
dissolver at 840F and 1500 psig.
The process produces a low-ash (0.1%), low-sulfur
(0.3%), solid fuel with a heating value of 16,000
Btu/lb.
The SRC-I fuel was envisioned as a boiler fuel to
replace natural gas and fuel oil.
SRC-I Process
 SRC-II Process

The SRC-I process was modied to eliminate a

number of processing steps and to produce an all-
distillate, low-sulfur fuel oil from coal rather than a
solid fuel.
In the SRC-II process, pulverized and dried coal is mixed
with recycled slurry solvent from the process.
The slurry mixture is pumped to reaction pressure
(140atm), preheated to about 700 to 750F, and fed into
the dissolver, which is operated at 820 to 870F.
The dissolver efuent is separated into vapor-and liquid-
phase fractions.
 SRC-II Process

The overhead vapor stream undergoes several stages

of cooling and separations, and the condensed liquid is
distilled to produce naphtha and a middle distillate oil,
which a reconverted to gasoline and diesel fuel,
respectively.
The gaseous products are puried to remove hydrogen
sulde and carbon dioxide, and the hydrogen-rich gas is
then recycled to there actor with make-up hydrogen.
The liquid-phase product acts as the solvent for the
SRC-II process.
SRC-II Process
 Costeam Process

The costeam process, investigated at the Pittsburgh

Energy Research Center (DOE) and the University of
North Dakota/Grand Forks Energy Research Centerwas
intended to produce low-sulfur liquid products from
lignites and subbituminous coals.
This process uses crude syngas containing about 50
to 60% carbon monoxide and 30 to 50% hydrogen, rather
than pure hydrogen.
The high moisture content of the low-rank coals
provides the water that is converted to steam.
 Costeam Process

Ground coal is slurried with recycled product oil from the

process.
The slurried coal is pumped to unit pressure (4000 psig),
mixed with syngas, heated to 750 to 840F, and maintained at
conditions for periods of 1 to 2 hours to liquefy the coal.
Severe operating conditions are required for the dissolution of
the lignite.
These operating conditions were a drawback for the process,
as long residence times and high pressures are costly and
present major engineering problems.
This process, although a potential candidate for liquefying low-
rank coals, was only tested in small-scale equipment.
 Catalytic Processes

The most important process of this group is the H-Coal

process, developed by Hydrocarbon Research, Inc. (HRI)
as an outgrowth of previous work on the hydrogenation of
petroleum fractions.
The development of this process was sponsored by the
ERDA and a large group of oil companies.
 H-Coal Process

In the H-coal process, pulverized coal is slurried with recycled

oil and, along with hydrogen, fed to an ebullated-bed reactor,
a feature that distinguishes this process from others.
Reactor conditions are normally in the range of 825 to 875F
and 2500 to 3500 psig.
The reactor contains a bed of catalytic particles, cobalt
molybdate on alumina oxide.
The products from the reactor include hydrocarbon gases, light
and heavy distillate oils, and bottoms slurry.
Variations of the processing scheme can produce fuel oil,
naphtha, synthetic crude, ammonia, and fuel gas.
Further processing can produce gasoline and jet fuel.
H-Coal Process
H-Coal Process
 H-Coal Process

In 1995, when it became an employee-owned company,

HRI changed its name to Hydrocarbon Technologies, Inc.
(HTI).
HTI has modified its process, now known as HTIs direct
coal liquefaction (DCL) process and shown schematically
in Figure 5-36, and it has gone from a single- to double-
stage reactor system.
 H-Coal Process

In the HTI DCL process, pulverized coal is dissolved in

recycled, coal-derived, heavy-process liquid at about
2500 psig and 800F while hydrogen is added.
Most of the coal structure is broken down in the first-
stage reactor.
Liquefaction is completed in the second-stage
reactor, at a slightly higher temperature and lower
pressure.
A proprietary GelCat catalyst is dispersed in the slurry
for both stages.
The process produces diesel fuel and gasoline.
H-Coal Process
 Donor Solvent Processes

The main representative of this process is the Exxon

donor solvent (EDS) process.
In a donor solvent process, the solubilization of the
coal is done by the hydrogen donor liquid, and
hydrogen molecules come from the donor liquid and
not gaseous hydrogen.
The donor liquid is then recycled and hydrotreated to add
hydrogen back into the donor liquid.
 Exxon Donor Solvent Process

In the EDS process, finely ground coal is mixed with the

donor solvent, and the coal is liquefied in a noncatalytic
tubular plug-flow reactor in the presence of molecular
hydrogen and a hydrogen-rich donor solvent.
The liquefaction reactor operates at 800 to 880F and
1700 to 2300 psig.
The products from the liquefaction reactor are separated
by distillation into light hydrocarbon gases, ranging
from methane to propane and methylpropane, a naphtha
fraction, a heavy distillate, and a bottoms fraction.
The naphtha and heavy distillate fractions are treated by
conventional petroleum-refining technology.
 Exxon Donor Solvent Process

About 85% of the naphtha is recovered as gasoline, and

about 50% of the heavy distillate is recovered as a
mixture of benzene, toluene, and xylenes.
Further processing of the heavy distillate produces
fractions comparable to jet fuel and heating fuel.
A portion of the heavy distillate is hydrotreated and
recycled to slurry the coal.
In addition, the bottoms are either coked in a fluid coking
plant or recycled to the liquefaction reactor.
Recycling to the liquefaction unit results in a dramatic
increase in the conversion of the coal to liquid products.
Exxon Donor Solvent Process
Exxon Donor Solvent Process