Reactions of Hydrogen Chloride with Carbonaceous Materials and the Formation of Surface Chlorine Species

Significance Statement

Evolution of Hydrogen Chloride (HCl) in industrial processes produces hazardous chlorinated organic compounds through secondary reactions with unburned carbon downstream of initial combustion sites. According to Stieglitz et al. (Chemosphere 1991, 23, 12551264), metallic chlorides present in unburned carbon works as source of chlorine as well as catalyst for formation of dioxins.

The role of unburned carbon formation of organochlorides is still unclear, however O2 gasification of carbonaceous substances such as CO or CO2 upon heating yields carbon active sites which works for formation of organic chlorides since they are more reactive than basal plane carbon.

In a recent article by Tsubouchi et al. 2016, and published in Energy & Fuels, the objective was to discover the mechanisms of HCl-Carbon interactions by investigating the effects of O2 activation and metal addition to the interaction thereby ascertaining the role of carbon active sites and some metal catalyst in the formation of organic chloride species.

In order to analyze the main objective of possible HCl-Carbon interactions, Tsubouchi et al. (2016) applied means of X-ray Photoelectron Spectrum (XPS) and Temperature-Programmed Desorption (TPD). XPS measurement was utilized in order to determine functional forms of chlorine present in pure and metal-doped activated carbons (AC) samples.

For the experiment set up, phenol resin was first carbonized in stream of Helium as carbon sample were denoted by AC-0, AC-50, AC-100, AC-150 with respect to their increasing surface area. Several AC-100 samples were loaded with either Potassium (K), Calcium (Ca) or transitional metals such as Copper (Cu) and Zinc (Zn) cations via an impregnation method using ethanol solution. The subsequent samples was immediately exposed to a stream of 100ppm of HCl in high-purity N2. The number of active sites of each surface of pure and metal-doped AC samples was also determined by CO/CO2-TPD method and all experiments were carried out in a cylindrical flow-type quartz reactor.

From the results, Tsibouchi et al. (2016) discovered that when AC-0. AC-50, AC-100 and AC-150 (without any metal cations added) were passed into a stream of 100ppm HCl/N2 immediately after heat treatment of 5000C, concentration of HCl decreased with respect to longer time periods. The amount of HCl which reacted with AC-150 sample was 8 times greater than AC-0 sample.

The rate of HCl reactions in HCl-treatment trials with 0.5 mass % of K/C, Ca/C. Cu/C and Zn/C specimen showed that K/C sample shared almost the same profile with AC-100 (when no metal cations were added) with initial increase with time on stream but decreased steeply after reaching a maximum at approximately 6min while Ca/C, Cu/C and Zn/C specimens decreased with an increasing time after 8-9 min. It can be inferred that metal cations increases the amount of HCl reaction concept for K+ with Zn/C having the highest increase of HCl reacted.

On investigation of the CO/CO2-TPD behaviors, AC-0 generated small amounts of CO and CO2 over the range of 150-2000C. AC-50, AC-100 and AC-150 specimens evolved CO at approximately 2000C and rate of CO formation increased rapidly beyond 4000C while CO2 formation started around 1500C reaching its shoulder peak at approximately 2500C and also CO2 formed increased remarkably at 4000C while CO2 formation which also increased significantly at the rate of 350-4500C depending on the metal species with Cu greatly influencing the rate of CO2 formation at approximately 3500C.

From XPS measurements to treat Cl forms in HCl treated carbon samples was seen that AC-100 and K/C solid lines generated a weak XPS signal binding energy range of 197-203eV with a peak maximum of 200eV while Ca/C, Cu/C and Zn/C showed broad peaks in range of 196-204ev with different peak maxima, Cl 2p3/2 XPS peaks of KCl, CaCl2, CuCl2, ZnCl2 and C6H5Cl appeared at 198.3, 198.5, 199.3, 198.5 and 200.5eV which shows that there is probability of both organic and inorganic  chlorides were present on surface of five carbon samples.

Deconvolution analysis of the five HCl-treated carbon samples showed the proportions of inorganic and organic chloride were 15-58 and 42-85mol% with Cl/C ratios in range of 1.6-4.4×10-3. The ratios obtained from Ca/C, Cu/C and Zn/C samples were 2.0-2.3 times the value without any addition which showed inorganic chlorides can promote the formation of organic chloride species.

Tsubouchi et al. (2016) conclude on the basis of discussed results that the addition of these metals promoted the formation of organic chloride forms. The results helps in understanding organic chemistry during high temperature combustion process and efficient methods developed in order to inhibit formation of hazardous chlorinated compounds.


Reactions of Hydrogen Chloride with Carbonaceous Materials and the Formation of Surface Chlorine Species. Advances in Engineering

About the author

Naoto Tsubouchi  is an associate professor in the Center for Advanced Research of Energy and Materials, Faculty of Engineering, Hokkaido University, Japan since 2011. I was born in Hokkaido, in 1973. I received my Ph.D. degree in engineering from Tohoku University in 2001.

Approximately 80 % of total primary energy supply depends on oil, coal and natural gas, and this dependency will be almost unchanged in the not-too-distant future according to a recent IEA (International Energy Agency) world energy outlook. It is thus probable that ultimately-efficient utilization of fossil fuels is the best way in order to reduce CO2 emissions in a carbon-constrained economy.

I have therefore been focusing every effort on fundamental research about advanced and novel technologies for heavy oil residues, low rank coals and low-valued natural gas.  

Journal Reference

Naoto Tsubouchi*1, Noriaki Ohtaka2, Yasuo Ohtsuka2 . Reactions of Hydrogen Chloride with Carbonaceous Materials and the Formation of Surface Chlorine Species. Energy Fuels, 2016, 30 (3), pp 2320–2327.

Show Affiliations
  1. Center for Advanced Research of Energy and Materials,Hokkaido University, Kita 13 Nishi 5, Kita-ku, Sapporo, Hokkaido 060-8628, Japan
  2. Institute of Multidisciplinary Research for Advanced Materials,Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai, Miyagi 980-8577, Japan


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