4th EucheMs chemistry congress

wednesday, 29-Aug 2012
s689
chem. Listy 106, s587–s1425 (2012)
inorganic Chemistry plus Young inorganic chemistry day
symposium on Co2 chemistry – i
o - 3 0 6
Co CAPture froM fLue GASeS: exiStinG
2
oPtionS And PerSPeCtiveS
t. KAtz 1 , i. CLAuSen 1
1 BASF SE, OASE Gas Treatment Excellence, Ludwigshafen,
Germany
Over the past 10-20 years, a variety of processes for
capturing carbon dioxide from flue gases have been developed.
In particular chemical absorption processes have meanwhile
reached a level of maturity that these processes nowadays can be
applied on an industrial scale.
The paper provides an overview over the most relevant
technologies and focuses on some key performance figures and
characteristics: purity of the processed streams, energy
consumption, solvent circulation rates as well as emissions and
product availability and process reliability are important
parameters, when it comes to process selection.
In public discussion, chemical absorption processes are
often criticized for their high energy consumption. With an
entropy evaluation, the paper will show, where the
thermodynamic minimum energy consumption will be, what level
can be realized under reasonable boundary conditions and how
this compared to today’s technologies. The approach is
independent on the type of process and can also be used to predict
the separation efficiency of e.g. adsorption or membrane
processes.
Atop, the latest developments to further improve the process
performance of carbon dioxide absorption will be presented and
some of the major challenges will be discussed.
Keywords: Chemisorption; Absorption;
symposium on Co2 chemistry – i
4 th EucheMs chemistry congress
o - 3 0 7
Co - inSertion into Si-n-BondS - A
2
MeChAniStiC Study
K. KrAuShAAr 1 , u. BÖhMe 1 , A. SChwArzer 1 ,
e. KroKe 1
1 TU Bergakademie Freiberg, Institute for Inorganic Chemistry,
Freiberg, Germany
CO may be used as starting material for chemical syntheses,
2
e. g. for the synthesis of urea, methanol, and several carbonates.
Hence, CO is mainly used as a C1 source. One of the several
2
[1] methods known for the activation of CO is the insertion into a
2
main group or transition metal nitrogen bond. [2] Most of the
literature focus on the reactions of Me SiCl with primary and
3
secondary amines, e. g. using the TMS substituent as directing
group in organic synthesis. [3] In contrast, we report here the use
of Me SiCl and a primary amine as starting materials for the
2 2
synthesis of diaminosilanes Me Si(NHR) . Subsequent
2 2
quantitative bis-insertion of CO yields the corresponding
2
[4, 5]
di(alkylcarbamoyloxy)dimethylsilanes Me Si(OCONHR) . 2 2
Diaminosilanes of the type (RHN) SiMe , obtained from
2 2
Me SiCl and primary amines, were subjected to a double
2 2
insertion of CO at room temperature to afford the
2
carbamoyloxysilanes. The latter reaction is exothermic and
proceeds with very good yields. To gain further insight into the
reaction mechanism of the CO insertion, we performed DFT
2
calculations with a simple model aminosilane, Me Si(NHMe) . 2 2 [6]
references:
1. D. Belli Dell‘Amico, F. Calderazzo, L. Labella,
F. Marchetti, Chem. Rev. 2003, 103, 3857.
2. C. A. Stewart, D. A. Dickie, M. V. Parkes, J. A. Saria,
R. A. Kemp, Inorg. Chem. 2010, 49, 11133.
3. M. J. Fuchter, C. J. Smith, M. W. S. Tsang, A. Boyer,
S. Saubern, J. H. Ryan, A. B. Holmes, Chem. Commun.
2008, 2152.
4. C. Wiltzsch, K.Kraushaar, A. Schwarzer, E. Kroke,
Z. Naturforsch., B: J. Chem. Sci. 2011, 66, 917.
5. C. Wiltzsch; J. Wagler; G. Roewer; E. Kroke,
Verfahren zur Herstellung von Oligo- und Polysiloxanen,
DE 10 2009 045 849.2, 2010.
6. K. Kraushaar et al., Organomet. 2012, submitted.
Keywords: Insertion; Silicon; Amines; Carbon dioxide
fixation; Density functional calculations;
AUGUst 26–30, 2012, PrAGUE, cZEcH rEPUbLIc