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Technology
Syngas
Production Syngas Production
There are several common non-gasi cation
Downstream
Conversion processes that are used to produce synthesis gas
Processes (syngas) on an industrial scale. They are 1) Partial
Oxidation, 2) Autothermal Reforming, and 3) Steam
Syngas Methane Reforming.
Cleanup

The
Gasi cation Partial Oxidation(POX)
Process POX is a chemical reaction that occurs when asub-
stoichiometricmixture of the feedstock and pure
Plasma
oxygen (O2) are reacted together, producing a syngas
Gasi cation
with a high concentration of hydrogen (H2). In
Underground re neries, POX is often used to convert heavy liquid
Coal hydrocarbon wastes to hydrogen, which is then used
Gasi cation in the re nery to process the incoming crude oil.

The feedstock is fed into the POX reactor (see gure

below), where the carbon in the feedstock is reacted
with oxygen in an exothermic reaction, forming
carbon monoxide (CO). Since there is a lack of oxygen,
the reaction does not complete to carbon dioxide
(CO2).

C + O2 CO

Typically, all or a portion of the CO then ows to a

water shift reactor, where the CO reacts with steam,
forming a mixture of CO and H2:

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CO + H2O CO2 + H2 (the overall H2/CO ratio in the

product stream is 1.6 to 1.7)

The CO2 is then removed using conventional acid gas

removal technologies, resulting in a high H2
concentration stream.

There are two primary types of POX systems: 1)

Thermal POX (TPOX), which occurs at >2,200F and is
used with high sulfur feedstocks, and 2) Catalytic POX
(CPOX), which uses low sulfur feedstocks with a
sulfur-sensitive catalyst, allowing the reactions to
occur in a lower temperature range of 1,475-1,650F,
which reduces energy consumption.

Steam Methane Reforming

Steam Methane Reforming, or SMR, uses natural gas
(methane) as the feedstock to produce a high H2
concentration syngas that can be used in re neries
and other industrial processes. In SMR, a heated
mixture of natural gas and steam ows through pipes
that are lled with a nickel-based catalyst (see gure
below).

The reforming reactions, which occur in a range of

1,470 - 1,740 F, are endothermic, and signi cant
external heat is required. This heat is typically
provided by burning additional natural gas outside the
tubes.

The reforming occurs in two reactors in series, with

approximately 90% of the methane converted in the
rst reactor, and the balance in the second reactor.
The overall reaction is as follows:

CH4 + H2O CO + 3H2 (the H2/CO ratio is 3:1)

The syngas stream then ows to a water shift reactor,

where additional steam reacts with the CO to form
CO2, and the water in the steam is converted to
additional H2.
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CO + H2O H2 + CO2

The CO2 in the stream is typically removed using

pressure swing adsorption(PSA). The PSA unit uses
molecular sieves to adsorb the impurities from the
syngas stream, resulting in a very high hydrogen
product stream with a H2/CO up to 5:1.

Autothermal Reforming
Autothermal reforming (ATR) combines thermal POX
and the reforming of low-sulfur natural gas in a single
reactor. The process was developed to produce syngas
from natural gas for making methanol, ammonia, and
Fischer-Tropsch liquids, due to its production of a
H2/CO ratio of 2:1. The ATR reactor is a refractory-
lined pressure vessel with a combustion chamber,
burner, and catalyst bed (see gure below).

In the reactor, natural gas is partially oxidized with O2

in a sub-stoichiometric environment in the following
simpli ed reaction:

CH4 + 3/2O2 CO + 2H2O

This reaction is exothermic, and provides the heat

required for the following intermediate reaction
where the CO2 that is produced combines with the
natural gas feedstock:

CH4 + CO2 2CO + 2H2 (the overall H2/CO ratio is

approximately 2:1)

POX, SMR or ATR?

The choice of which syngas production process to use
depends on many factors:

Type of feedstock
Gaseous compounds - natural gas and
naphtha
Liquids - heavy, liquid hydrocarbon re nery
wastes such as asphalt, sludges, emulsions

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Solids - coal, pet coke, biomass, and solid

wastes
Cost of feedstock
Liquid re nery wastes, at no cost
Natural gas at low cost (depends on current
market prices)
Pet coke from adjacent re nery, at low or no
cost
Negative cost municipal solid waste with
tipping fee
Cost to use waste feedstock is less than its
disposal cost
Downstream use
The downstream processes that use syngas
require speci c values or ranges for the
H2/CO ratio in the syngas.
Methanol = 2:1
Fischer-Tropsch liquid fuels = 2:1
Gas to liquids = 2:1
Acetic acid = 1:1
Ammonia = pure H2, no CO
When using natural gas as the feedstock,
either POX or SMR can be used. However,
POX and ATR both require the use of pure
oxygen (typically from an air separation
unit), while SMR does not.
For CO and CO-based chemicals, POX
provides the lower H2/CO ratio needed
For H2based chemicals, SMR provides the
high H2/CO ratio needed
POX is more feedstock exible (especially
for heavy liquid hydrocarbons), while SMR is
speci cally used for natural gas (methane)

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