Producer gas and syngas

1. What is Producer gas?

 Producer gas is mixture of gases produced by gasification of organic
material like Biomass, Municipal solid waste etc. Producer gas is composed
of mainly Carbon dioxide (CO2), Carbon monoxide (CO), Hydrogen (H2),
Methane (CH4) and Nitrogen (N2).
 Producer gas is mixture of flammable gases (CO, H2) and non-flammable
gases (CO2, N2) Produced by passing air or mixture of air and steam
through a burning bed of solid fuel(partial combustion) such as coal, coke,
wood and biomass.
 In general, Producer gas has low calorific value. However, it also depends
upon composition of producer gas. Typically Producer gas obtained from
coke contains 55% N2, 27% CO, 12%H2, 5%CO2, and 0.5% CH4 by volume;
such gas typically has heating value of about 5000 KJ/m3.
 The exact composition of producer gas depends upon the type of fuel,
composition of the air-steam blast and operating conditions.

2. What is syngas?
 Syngas is mainly composed of Carbon monoxide (CO) and Hydrogen (H2) and
trace amount of carbon dioxide (CO2).
 Syngas can be produced from many sources such as natural gas, coal,
biomass or any hydrocarbon feedstock by reacting with steam or oxygen.
 Syngas played important role as intermediate in production of hydrogen,
Ammonia, methanol, synthetic natural gas (SNG CH4) and liquid biofuel such
as synthetic diesel (via Fischer-Tropsch synthetic).

The main difference between producer gas and syngas lies in their
composition. It is noted that syngas has higher heat content as compared to
producer gas.
Applications for Producer gas/Syngas:-
As we know Producer or syngas is very important intermediate gas for many
synthesis processes. Producer gas/syngas can also use as a fuel. Producer
gas/Syngas has wide range of applications in chemical Industry. List of those
applications are given below:

 Power Generation
 As a fuel or for heating purpose in furnace
 Production of Hydrogen
 Production of Methanol
 Production of Ethanol
 Dimethyl ether Production
 Synthetic Natural Gas(SNG)
 Fischer-Tropsch synthesis
 Production of Gasoline or Diesel

As discussed, there are many applications in which synthesis gas can be

utilized. There are no of chemical produce from syngas as shown in
figure below:
Figure 1: output pathways from syngas
We will discuss each of these applications in details later on. Before going
into details, it is important to note that to use the gas coming out from
gasifier as synthesis gas, there are several properties it must possess which
are given below:

1) H2:CO Ratio
2) Amount of inert in gas such as Nitrogen
3) Amount of methane and higher hydrocarbon
4) Catalyst Poisons components like sulphur, chlorine and Nitrogen.
5) Operating Pressure

Synthesis gas consists mainly of hydrogen and carbon monoxide, in some

cases small amounts of carbon dioxide (methanol synthesis) or methane
(BioSNG) are also present. For most synthesis a H2: CO ratio of 2 is required.
This ratio is normally adjusted in a separate catalytic reactor before the
synthesis reactor, where some CO is converted to Hydrogen by the water-gas
shift reaction. If the gasifier produces the desired H2: CO ratio, the exothermal
water-gas shift reaction can be avoided, which reduces investment and
operation costs and also increases the efficiency.

Impurities like nitrogen act as inert during the synthesis and their
concentration have to be as low as possible. The inerts reduce the partial
pressure and by this effect reduce the conversion. Especially for synthesis
reactions, where the product is separated as a liquid and where a recycle of
remaining unconverted gas is done (e.g., methanol), the inerts have to be
taken away as they would otherwise be accumulated. Also for production of
BioSNG the inerts have to be below 1 volume%, as otherwise the heating
value of the BioSNG will not fulfil the requirements of natural gas.

Methane and higher hydrocarbons normally act as inert during the synthesis
reaction, so they have to be treated similar to inerts. These components are
mainly present in fluidized bed reactors and not in high temperature
gasification. As the heating value of the hydrocarbons is much higher than
that of H2 and CO, a small amount of hydrocarbons already present in the gas
can contain most of the energy of the synthesis gas. So the overall conversion
from biomass to final product (e.g., FT liquids) is reduced by the small
amounts of hydrocarbons that are already produced in the gasifier. So in most
cases the hydrocarbons are converted to H2 and CO in a reformer to maximize
the conversion from biomass to the final desired product. The only exception
is the production of BioSNG. Here a high content of methane and nontar
hydrocarbons in the synthesis gas are favoured, as then the highest
conversion efficiency to BioSNG is achieved.

Catalyst poisons deactivate the synthesis catalyst and have to be removed to

very low levels. The most well-known poison is sulfur, which can be in form of
H2S, COS, mercaptans, or thiophens in the synthesis gas. The organic sulfur
components are mainly present in fluidized bed gasifiers, and not in high
temperature gasification. So the removal technology has to be adapted to the
type of the sulfur components.

Almost all synthesis reactions are under elevated pressure and the synthesis
gas has to be compressed during the gas treatment. By the choice of a
pressurized gasifier, the electricity consumption of the compressor can be
reduced or avoided. Until now only oxygen or oxygen–steam blown gasifiers
were operated under elevated pressure, in which case the investment and
Operation costs for an air separation unit have to be taken into account. For
this reason in small scale (<100MW fuel input), mainly indirect atmospheric
gasifiers are discussed to avoid the costs of the oxygen production.
As we discussed, I should focus on mainly conversion from producer gas to
chemical such as methanol, ethanol, dimethyl ether and so on rather than
heat and power applications of producer gas. We will discuss each of
applications in detailed manner:

1) Production of Methanol:
Methanol is simple alcohol with chemical formula of CH3OH. Methanol can be
used as fuel for vehicles as well. Methanol is important feedstock in chemical
industry to produce other chemicals such as Formaldehyde, DME etc.

Methanol production from syngas classified mainly into five parts:

1) Removal of inert such as nitrogen and other hydrocarbon from output

gas from gasifier
2) Preparation of appropriate H2/CO ratio via water gas shift reaction in
presence of catalyst in fixed bed reactor
3) Removal of excess concentration of CO2 through separation
technique(PSA, absorption, Adsorption)
4) Catalytical treatment of gas to produce methanol and water(byproduct)
5) To separate the liquid mixture of Methanol and water(Distillation)

First of all, output gas from gasifier must possess certain properties as we
discussed in earlier section. Gas undergoes various physical and chemical
treatments in order to achieve such properties. In general, mixture of iron and
chromium oxide (92% Fe2O3 and 8% Cr2O3) used as catalyst for water gas shift
reaction and mixture of copper and zinc oxide used as catalyst for
methanation process.

There are total three reactions involved in production of methanol from

syngas.

CO + H20 → CO2 + H20 (WATER GAS SHIFT RXN)

CO + 2H2 ↔ CH3OH (Hydrogenation)

CO2 + 3H2 ↔ CH3OH + H20 (Hydrogenation)

As these reactions are exothermic, higher pressure and lower temperature
favours equilibrium conversion according to Le Chatelier principle.

2) Production of BIO Synthesis Natural gas:

Natural gas that is produced from coal or biomass is known as ‘synthetic
natural gas. Production of BIOSNG from syngas classified into four parts:

1) Removal of inert and poisonous component (sulphur) from output gas

from gassifier
2) Catalytic treatment to achieve H2/CO ratio of 3 for production of
BIOSNG
3) Catalytic treatment (methanation) to produce Methane and water
4) To separate the Methane and water through physical treatment

Typical Reaction of Methanation is take place in presence of Ni catalyst. The

reaction involved is given below:

CO + 3H2 → CH4 + H2O

There is one main difference in the synthesis Natural gas with other synthesis
process is amount of methane present in the syngas from gasifier which don’t
need to remove from it. In fact, higher content of methane favoured
production of BIOSNG.

3) Production of hydrogen from syngas:

As of now, Almost 96% of hydrogen production is from thermochemical
conversion from fossil fuel (Natural gas). The main process of production of
hydrogen from syngas is steam reforming. As authors mentioned, there are
total two plant layout to produce hydrogen from syngas.

Gasification technology and choice of raw material played critical role in

production of hydrogen. clean producer gas goes to steam reforming unit to
produce hydrogen. But prior to steam reforming step, CO2 removal unit is
done by monoethanolamine scrubber. The Purified methane and hydrogen
rich gas then used as feed for steam reforming unit.

In general, Ni oxide is used as catalyst for steam reforming unit and reaction
involved is:

CH4 + H20 → CO + 3H2

CO + H20 ↔ CO2 + H2

4) Production of ethanol from syngas:

Ethanol is alcohol and has chemical formula of CH3CH2OH.

Anaerobic Bacteria are able to grow on syngas components, thus forming

ethanol and acetate. The bacterial culture has able to convert CO, CO2 and H2
into ethanol.

In this process, the gasification reactor is best fed with pure oxygen in order
to decrease the equipment size and, most importantly, not to dilute the
outlet stream (as this would negatively affect the mass transfer in the
fermentation reactor). Before entering the reactor, the gas is cooled down to
39 C with generation of steam. The fermentation step is carried out by some
bacteria which are capable of digesting CO, H2 and CO2 and, as result of the
acetogenic pathway, produce ethanol and acetic acid. Reactions involved in
this pathway are

6CO + 3H2O → CH3CH2OH + 4 CO2

6H2 + 2CO2 → CH3CH2OH + 3H2O

Bubble reactor or packed column reactor is adopted to maximize surface area

and increase the gas-to-liquid mass transfer rate.
5) Production of Hydrocarbon from syngas (Fischer
Tropsch):
Fischer–Tropsch synthesis is a set of catalytic processes for converting
synthesis gas (mixture of carbon monoxide and hydrogen) into liquid
hydrocarbons. Generally, there are three main steps in the Biomass to Liquid
via Fischer–Tropsch (BTL-FT) synthesis. Biomass is firstly converted into
biomass-derived syngas (bio-syngas) by gasification. In a second step, a
cleaning process is applied to the bio-syngas in order to remove impurities,
resulting in clean bio-syngas which meets the Fischer–Tropsch synthesis
requirements. Finally, the cleaned bio-syngas is then conducted into Fischer–
Tropsch catalytic reactor to produce green gasoline, diesel and other clean
biofuel.

The reactions in the Fischer–Tropsch process are generally described as the

following:

2n+1) H2 + nCO → CnH2n+2 + nH2O

2nH2 + nCO → CnH2n + nH2O

Commercially available FT reactors nowadays have two different temperature

ranges. The high temperature FT (HTFT) reactor runs with iron catalysts at
around 340°C, and is used to produce olefins and gasoline. The low
temperature FT (LTFT) reactor uses iron or cobalt based catalysts at around
230 °C, and is used to produce diesel and linear waxes.

6) Production of Dimethyl ether:

Dimethyl ether is generally produced from dehydration of methanol. As we
discussed about methanol in detail, syngas has to follow same procedure up
to methanol and then followed by dehydration unit.
References:
1) Reinhard Rahuch et. al. “Biomass gasification for synthesis production
and application of syngas”, WIREs Energy Enviorn, July 2014.
2) Jin Hu et. al. “Application of Fischer Trospch synthesis in biomass to
liquid conversion”, Catalyst, 2012.
3) Luiz.A.H. et. Al. “Biomass gasification for ethanol production”, DOI
10.1007/978-0-387-92740-4_3, 2011.
4) Tapas Kumar Patra et. al. “Process simulation for hydrogen rich gas
from producer gas using HTS catalysis”, Energy,2019.
5) Sammy Sadaka “Gasification, Producer gas, Syngas”, Agriculture and
Natural resources, University of Arkansas system.
6) Loenie.E.Lucking “Methanol Production from syngas”.