Reduced Gas-phase Sulphur Chemistry in

Recovery Boilers and BLG Processes

a work in progress report
Linda Pommer1, Anders Nordin1, Erik Rosn1
Energy Technology and Thermal Process Chemistry, Ume University

Background

The gas phase reduced sulphur
chemistry in black liquor combustion and
gasification processes is not previously
well studied and include several potential
gas phase S-species. In addition, the
fundamental thermodynamic data of COS
(g) is associated with significant
uncertainties.
Method
reaction products are controlled by
varying the temperature and initial
concentrations of H2S and CO2. The
equilibrium concentrations of e.g. H2S,
CO2, CO, COS, S2, and H2 are
determined, and are compared with
corresponding chemical equilibrium
modelling results. The impact of the
study when more data have been
collected is validation and improvement
of existing thermodynamic data.
The equilibrium concentration of COS at
850C was for example found to be 56
ppm for initial CO2 and H2S concen-
trations of 1000 ppm. This is closest to
the calculated results using thermo-
chemical data from Terres, but still 2.1
times higher. Further systematic experi-
mental work and system evaluation will
be performed to improve existing
thermodynamic data for COS (g).

A careful systematic experimental study

was initiated in which controlled synthetic 300000
CO2
atmospheres containing H2S and CO2 is Equilibrium model calculations
250000
equilibrated in an isothermal plug flow H2S

Response (c/s)
reactor made of alumina. The resulting Three sets of data were used in the 200000
gas phase compositions are analysed equilibrium calculations - the Fact-, and
150000
using a molecular beam mass spectro- SGTE databases and data for COS
meter (MBMS, Hiden HPR60 system). By from Terres1. The calculations were 100000 S
HS
sampling the equilibrated atmospheres at performed for the same eight initial CO

conditions as for the experiments. 50000

high temperatures (850-1000C) using COS
the MBMS, the species present are 0
instantly quenched and hence measured 1

8
:4

:5

:0

:1

:2

:2

:3

:4
in their high-temperature states and
30

40

51

01

11

21

31

41
60
:

:
01

01

01

02

02

02

02

02
concentrations.
50 time (hh:mm:ss)
Formed COS (ppm)

40
Figure. Gas-phase equilibrium composition of the
reactor gas (850C). Initial levels of H2S and CO2
30
Introduction of gases added were 1000 ppm.
20
Reactor
10

0
Fact SGPE Terres Experimental
data

Heating elements
Figure. Formed concentrations of COS (ppm) in 2-5 times more COS
equilibrium calculations using different databases
compared to results from experiments.
formed in experiments
compared to equilibrium
results, depending on
temperature and
Preliminary experimental results source of data!
MBMS

Experiments have so far been

performed for a few different initial
atmospheres using Helium as carrier
gas.
The MBMS is calibrated using known References
concentrations of the gases of interest.
Attainment of equilibrium is secured by 1. Terres, E., Weseman, H. ber Gleichgewichts-
messungen der Teilreaktionen bei der Umsetzung
varying residence times as well as
von Schwefelkohlenstoff mit Wasserdampf im
attaining equilibrium from different Temperaturgebiet von 350C bis 900C.
directions. The concentrations of Angewandte Chemie 1932, 45, 795-832.

Energy Technology and

Thermal Process Chemistry
Ume University
SE-901 87 Ume, Sweden
Phone: +46 (0)90-786 53 19
Fax: +46 (0)90-786 91 95
E-Post: linda.pommer@chem.umu.se
linda.pommer@chem.umu.se anders.nordin@chem.umu.se erik.rosen@chem.umu.se