CHEMICAL VALORIZATION OF CO2 FROM STEEL PLANTS AND COKE OVENS

W. Uribe-Soto1, 2, J.-F. Portha1, 2, J.-M. Commenge 1, 2, L. Falk 1,2

1Universit

de Lorraine, LRGP, Laboratoire Ractions et Gnie des Procds, UMR 7274, Nancy, F-54000, France
2 CNRS , LRGP, Laboratoire Ractions et Gnie des Procds, UMR 7274, Nancy, F-54000, France

INTRODUCTION
The steel industry is the main generator of CO2 among the different industrial sectors. That is why efforts are being made, among which some resulted in reductions of CO2
emissions or in the use of the Carbon Capture and Storage (CCS) process. But the CO2 should be seen as a renewable carbon source that may be transformed into products with
high added value. In this context, the VALORCO (VALOrization and Reduction of CO2 emissions in the industry) project has been launched. The VALORCO project considers
different pathways of CO2 valorization through its chemical transformation. This particular study focuses on the thermochemical conversion and valorization of CO2. Here, some
preliminary results are presented.

THE VALORCO PROJECT

The Steelmaking Process

The Valorco Project

Blast Furnace + Basic Oxygen Furnace

General objective

Purification/Separation
Processes

To achieve a reduction of 30% in the current

CO2 emissions.

Top Gas Recycled Blast

Furnace
Mineral Carbonation

CO2
VALORIZATION

Fermentation Process
CO2 capture by
methanation intensification

Thermochemical
Conversion
Source : http://www.jisf.or.jp/course50/tecnology03/index_en.html

Coke Oven Gas Blast Furnace Gas Basic Oxygen Furnace

(COG)
(BFG)
Gas (BOFG)
Flow (Nm3/h)
Compound
CO2
CO
H2
CH4
CxHy
N2
Ar + O2

40 000
1,2
4,3
63,0
22,5
2,5
6,0
0,2

730 000
Composition (% mole)
22,5
24,4
3,8
0,0
0,0
48,5
0,6

ALTERNATIVES
TO COKE USE

VALORCO
PROJET

Electrochemical
Conversion

35 000

INDUSTRIAL
INTEGRATION OF
THE RESULTS

20,9
56,3
3,3
0,0
0,0
18,8
0,7

Main tasks of the thermochemical conversion study

The identification, evaluation and comparison of the valorization pathways,
the design and optimization of the selected process.

STRUCTURE OF THE VALORIZATION SCENARIO

BFG
BOFG
COG
H2O

Working Assumptions

Water Gas Shift

Reactor

Steam Methane
Reformer

Total conversion for all the reactions,

Excess of CO2
Separation of
Inerts

High added
value product
H2O

Reaction/
Separation

Perfect separation of the compounds,

The increase in the supply of the
product has no impact on its price.

N2, Ar, O2

PRELIMINARY RESULTS
Example of fact sheet constructed

Multi-criteria comparison of the considered high added value products

Product
Urea
Methanol
Acetic Acid
Dimethyl ether
Formaldehyde
Gasoline
Dimethyl carbonate
Methane
Ethanol
Formic Acid

Market
(kton/an)
184 000
75 000
6 500
6 500
26 000
900 000
2 000
1,5 . 1011
70 000
720

% of Potentially
covered market
1
2
31
16
8
0
99
0
1
846

Price
(/ton)
270
450
450
730
700
1400
730
560
985
550

Potential revenues % of carbon

(M/year)
valorized
715
30
636
30
894
44
741
30
1 390
44
864
30
1 450
44
297
22
1 000
30
3 349
89

TRL*
9
9
9
8
7
9
6
6
5
5

*Technology Readiness Level

CONCLUSION
Several products can be synthesized from CO2: 10 products have been retained as the most promising paths for further study. A variety of information for each product has been
collected. The studied scenario includes the possibilities of hydrogen generation, using Steam Methane Reforming (SMR) or Water-Gas Shift reaction (WGSR). Finally, a
calculation of the maximum amount of each product which can be synthesized according to the available hydrogen has been made. This quantity along with the collected
information enabled the calculation, for each product, of the percentage of the potentially covered market, potential revenues as well as the percentage of carbon valorized.
These three parameters, along with the TRL, are eliminatory criteria that exclude some products and enable classification of all products.

ACKNOWLEDGEMENTS
The authors thanks the Agency for the Environment and Energy Management (ADEME) for funding this research project.
Large Volume CO2 Utilization : Enabling Technologies for Energy and Resource Efficiency. Lyon, Sept. 25-26 , 2014