Assignment-3

Pyrolysis
Harikrishnan K V

Wednesday 13th December, 2023

1
Contents
1 Pyrolysis 3
1.1 Pyrolysis Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.2 Solid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.3 Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.2 Types of Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 slow Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4 Fast pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.5 PYROLYZER TYPES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5.1 Fixed-Bed Pyrolyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5.2 Bubbling fluidized bed pyrolyzer . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5.3 Circulating fluidized bed pyrolyzer . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5.4 Rotating cone reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5.5 Ablative reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.5.6 Vacuum reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

List of Figures
1 Pyrolysis process in a biomass particle. . . . . . . . . . . . . . . . . . . . . . . . . 3
2 Fixed bed pyrolysis plant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3 Bubbling fluidized bed pyrolyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4 Circulating fluidized bed pyrolyzer . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5 Rotating cone reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
6 Ablative reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7 Vacuum reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1 Pyrolysis

1 Pyrolysis
Pyrolysis involves rapid heating of biomass or other feed in the absence of air or oxygen at a
maximum temperature, known as the pyrolysis temperature, and holding it there for a specified
time to produce noncondensable gases, solid char, and liquid product. The liquid product is of
primary interest in pyrolysis. The nature of its product depends on several factors, including
pyrolysis temperature and heating rate.

Figure 1: Pyrolysis process in a biomass particle.

The initial product of pyrolysis is made of condensable gases and solid char. The condens-
able gas may break down further into noncondensable gases ( CO, CO2 , H2 , and CH4 ), liquid,
and char. This decomposition occurs partly through gas-phase homogeneous reactions and
partly through gas solid-phase heterogeneous thermal reactions. In gas-phase reactions, the
condensable vapor is cracked into smaller molecules of non condensable permanent gases
such as CO and CO2 .

1.1 Pyrolysis Products

Pyrolysis involves a breakdown of large complex molecules into several smaller molecules. Its
product is classified into three principal types:

1. Liquid (tars, heavier hydrocarbons, and water)

2. Solid (mostly char or carbon)

3. Gas (e.g., CO2 , H2 O, CO, C2 H2 , C2 H4 , C2 H6 , C6 H6 ).

1.1.1 Liquid

It’s also called tar, bio-oil, or biocrude. Bio-oil is a black, sticky fluid that contains up to
20% water and is mostly made up of similar phenolic chemicals. It is made up of oxygen,
water, and complicated molecules. The cellulose, hemicellulose, and lignin parts of biomass
are broken down and depolymerized to make bio-oil. It is a microemulsion with a continuous
phase of products from breaking down cellulose and hemicellulose and an irregular phase

3
1 Pyrolysis 1.2 Types of Pyrolysis

of macromolecules that are formed when lignin is heated. hydroxyaldehydes, hydroxyketones,

sugars, carboxylic acids, and phenolic compounds are some of the chemicals that can be found
in bio-oil.

1.1.2 Solid

Biochar is the solid product obtained from the process of pyrolysis. The composition of this
substance is predominantly carbon (about 85%), with the possibility of possibly containing
trace amounts of oxygen and hydrogen. Biomass has a significantly lower amount of inorganic
ash compared to fossil fuels. The lower heating value (LHV) of biomass char is around 32
MJ/kg. This value is significantly more than that of the original biomass or its liquid derivative.
It exhibits a high pore surface area.

1.1.3 Gas

Primary decomposition of biomass produces condensable and noncondensable gases, with

vapors condensing upon cooling and noncondensable gases like carbon dioxide and methane.
Secondary gases are produced through secondary cracking at higher temperatures, resulting
in a mixture of primary and secondary gases. The heating values of pyrolysis gas are higher
than those of bio-oil, raw biomass, and fossil fuels.

1.2 Types of Pyrolysis

Based on the heating rate, pyrolysis may be broadly classified as slow and fast. It is considered
slow if the time, theating, required to heat the fuel to the pyrolysis temperature is much longer
than the characteristic pyrolysis reaction time, tr

• Slow pyrolysis: theating>tr

• Fast pyrolysis: theating<tr

1.3 slow Pyrolysis

Carbonization is a slow pyrolysis process that focuses on producing charcoal or char. It is the
oldest form of pyrolysis and has been used for thousands of years. The process involves heating
biomass slowly to a low temperature ( ≈ 400◦ C) over an extended period, allowing sufficient time
for the conversion of condensable vapor into char and noncondensable gases. Conventional
pyrolysis involves all three types of pyrolysis products (gas, liquid, and char) and a product
residence time of minutes.

1.4 Fast pyrolysis

The main goal of fast pyrolysis is to get as much liquid or bio-oil as possible. It heats up so
quickly that the waste hits the highest temperature for pyrolysis before it breaks down. If bio-oil
is what you want, the peak temperature should be below 650◦ C, but the heating rate can go as
high as 1000–10,000C/s. Of course, if making petrol is the main goal, the highest temperature
can reach 1000◦ C. Fluidized beds can be used to burn things quickly. This process helps make
more liquid by having four important parts:

• a very fast heating rate;

• a reaction temperature between 425 and 600C;

4
1 Pyrolysis 1.5 PYROLYZER TYPES

• a short dwell time (about 3 seconds) for the vapour in the reactor;

• the product gas quickly going out of the system.

1.5 PYROLYZER TYPES

1.5.1 Fixed-Bed Pyrolyzer

Figure 2: Fixed bed pyrolysis plant.

Fixed-bed pyrolysis, operating in batch mode, is the oldest pyrolyzer type. Heat for the
thermal decomposition of biomass is supplied either from an external source or by allowing
limited combustion as in a beehive oven Figure 2. The product may flow out of the pyrolyzer
because of volume expansion while the char remains in the reactor. In some designs, a sweep
gas is used for effective removal of the product gas from the reactor. This gas is necessarily
inert and oxygen free. The main product of this type is char owing to the relatively slow heating
rate and the long residence time of the product in the pyrolysis zone.

1.5.2 Bubbling fluidized bed pyrolyzer

Figure 3: Bubbling fluidized bed pyrolyzer

5
1 Pyrolysis 1.5 PYROLYZER TYPES

Figure 3 shows a bubbling fluidized-bed pyrolyzer. Crushed biomass (2-6 mm) is fed into a
bubbling bed of hot sand or other solids. The bed is fluidized by an inert gas such as recycled
flue gas. Intense mixing of inert bed solids (sand is commonly used) offers good and uniform
temperature control. It also provides high heat transfer to biomass solids. The residence time
of the solids is considerably higher than that of the gas in the pyrolyzer. The required heat
for pyrolysis may be provided either by burning a part of the product gas in the bed or by
burning the solid char in a separate chamber and transferring that heat to the bed solids. The
pyrolysis product would typically contain about 70-75% liquid on dry wood feed. As shown
in the figure, the char in the bed solids acts as a vapor-cracking catalyst, so its separation
through elutriation or otherwise is important if the secondary cracking is to be avoided to
maximize the liquid product. The entrained char particles are separated from the product gas
using single- or multistage cyclones. A positive feature of a bubbling fluidized-bed pyrolyzer is
that it is relatively easy to scale up.

1.5.3 Circulating fluidized bed pyrolyzer

Figure 4: Circulating fluidized bed pyrolyzer

The CFB pyrolyzer(Figure 4) is a larger, faster-moving system that works similarly to boiling
fluidized beds, but with a larger bed and a "fast bed" hydrodynamic mode. It allows for high
velocity and good mixing, allowing for the movement of biomass. The system also allows for
easy separation and burning of char in an external fluidized bed. The ultrarapid fluidized-bed
pyrolyzer, created at the University of Western Ontario, is likely where rapid thermal pyrolysis
(RTP) originated. The system uses a riser reactor, heating biomass to 500°C and cooling it
quickly, allowing for up to 83% wood liquid output.

1.5.4 Rotating cone reactor

In this process, biomass particles are fed into the bottom of a rotating cone (360-960 rev/min)
together with an excess of heat-carrier solid particles (Figure 5). Centrifugal force pushes
the particles against the hot wall; the particles are transported spirally upward along the
wall. Owing to its excellent mixing, the biomass undergoes rapid heating (5000 K/s) and is
pyrolyzed within the small annular volume. The product gas containing bio-oil vapor leaves
through another tube, while the solid char and sand spill over the upper rim of the rotating
cone into a fluidized bed surrounding it, as shown in Figure 5. The char burns in the fluidized
bed, and this combustion helps heat the cone as well as the solids that are recycled to it to

6
1 Pyrolysis 1.5 PYROLYZER TYPES

Figure 5: Rotating cone reactor

supply heat for pyrolysis. Special features of this reactor include very short solids residence
time (0.5 s) and a small gas-phase residence time (0.3 s). These typically provide a liquid yield
of 60-70% on dry feed. The absence of a carrier gas is another advantage of this process. The
complex geometry of the system may raise some scale-up issues.

1.5.5 Ablative reactor

Figure 6: Ablative reactor

This process, shown in Figure 6, involves creation of high pressure between a biomass
particle and a hot reactor wall. This allows uninhibited heat transfer from the wall to the
biomass, causing the liquid product to melt out of the biomass the way frozen butter melts
when pressed against a hot pan. The biomass sliding against the wall leaves behind a liquid
film that evaporates and leaves the pyrolysis zone, which is the interface between bio-mass
and wall. As a result of high heat transfer and short gas residence time, a liquid yield as high
as 80% is reported. The pressure between biomass and wall is created either by mechanical
means or by centrifugal force. In a mechanical system, a large piece of biomass is pressed
against a rotating hot plate.

7
1 Pyrolysis 1.5 PYROLYZER TYPES

Figure 7: Vacuum reactor

1.5.6 Vacuum reactor

A vacuum pyrolyzer, as shown Figure 7, comprises a number of stacked heated circular plates.
The top plate is at about 200◦ C while the bottom one is at about 400◦ C. Biomass fed to the
top plate drops into successive lower plates by means of scrapers. The biomass undergoes
drying and pyrolysis while moving over the plates. No carrier gas is required in this pyrolyzer.
Only char is left when the biomass reaches the lowest plate. Though the heating rate of the
biomass is relatively slow, the residence time of the vapor in the pyrolysis zone is short. As a
result, the liquid yield in this process is relatively modest, about 35-50% on dry feed, with a
high char yield. This pyrolyzer design is complex, especially given the fouling potential of the
vacuum pump.