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Trends and Views in the

Development of Technologies for
Chlorine Production from
Hydrogen Chloride

Sumitomo Chemical Co., Ltd.
Basic Chemicals Research Laboratory
Hiroyuki ANDO
Kohei SEKI
Carlos KNAPP*

Process & Production Technology Center
Norihito OMOTO

Sumitomo Chemical Co., Ltd. has developed a catalytic process that is highly recognized and applied worldwide
as a technology for recycling the hydrogen chloride generated as by-product in isocyanate plants into chlorine. In
this article we outline the trends and views in the development of various technologies for chlorine production
from hydrogen chloride, and present the recent advances in catalyst technology for the Sumitomo Chemical process.

This paper is translated from R&D Repor t, “SUMITOMO KAGAKU”, vol. 2010-II.

ever, the expansion in demand for vinyl chloride


monomers is smaller than that for isocyanates, and in
Chlorine (Cl2) is used as a starting material for products such as polyvinyl chloride monomers, isocyanates

the future we can expect that the excess of HCl will increase further.

(such as TDI and MDI), epichlorohydrin and various

In addition, Cl2, which is a starting material, is nor-

fluorocarbons. However, for example in the case of

mally produced by salt electrolysis, but since the expan-

toluene diisocyanate (TDI), which is manufactured ac-

sion of the demand for chlorine is greater than that of

cording to the following formulas (1) and (2), 4 moles

the demand for the caustic soda (NaOH) produced

of hydrogen chloride (HCl) are produced as a byprod-

along with it, there is a danger that the demand balance

uct for each 1 mole of TDI.

between Cl2 and NaOH will collapse.
Under these circumstances, technology for convert-

CO + Cl2 → COCl2


ing the HCl produced as a byproduct to Cl2 and reusing
it not only helps in effective use of excess HCl, but is

CH3C6H3(NH2)2 + 2COCl2
→ CH3C6H3(NCO)2 + 4HCl


also helpful to balance the salt electrolysis. Since, in
turn, this leads to conser vation of resources and energy, it has been studied for 100 years.

Approximately half of the 42 million tons of Cl2 pro-

In this article, we report on trends in the processes

duced annually is estimated to end up as HCl by-prod-

for producing chlorine from HCl and also introduce

uct generated in the way described above, or as various

new, improved technology for the Sumitomo Chemical

other chlorides.1)

HCl oxidation process which has been licensed to sev-

Normally, the HCl produced as a byproduct is di-

eral companies in Japan and overseas.

rectly sold as 35% aqueous hydrochloric acid or used as
the starting material for oxychlorination of vinyl chlo-

Method for Producing Chlorine from HCl and

ride monomers, while surplus amounts are disposed of

Its Features

using methods such as neutralization treatments. HowMethods for producing Cl2 from HCl are roughly divided in three; electrolysis processes, oxidizing agent

* Present post : Organic Synthesis Research Laboratory

recirculation processes, and catalytic oxidation.


HCl gas electrolysis process ing material is absorbed in water.5) The elementary reactions are shown in equations (3)– (7). which in turn reduces the electrolysis HCl gases that are obtained are dried with sulfuric acid. the large amount of electric O2 power that is consumed is still a problem. and since its plant at the Shanghai Industrial Park in 2008.000 ton per year demonstration the 1990s using a demonstration plant. then reach the cathode to be reduced to H2. The HCl and surface of the anode. HCl and inert gases are separated and product trolysis vessel. electrolysis process. and the 17% aqueous hydrochloric acid and Ru is used for the electrolysis membrane. 1/2O2 + 2e– 2H+ H+ H2O 3. Evaluations were carried out in voltage. Fig. In terms of the trends in the development of this Dilute hydrochloric acid is supplied to the cathode to technology. and the complete reaction is shown in equation (8). having as its main features the use of nitro- Bayer DeNora Process with ODC Conventional Process Fig. producing chlorine gas.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride 1. The conversion ratio a porous catalyst containing noble metals such as Pt for HCl is 20%. Uhde and DeNora) and DeNora have jointly developed The HCl conversion ratio is 70 – 85%. membrane. Bayer been no report of its industrialization. there is the advantage of the HCl ab- proximately 30% by using an oxygen depolarized cath- sorption process being unnecessary. but since the HCl a technology that can reduce power consumption by ap- is reacted as a gas. The gen- water present in the Cl2 gas generated at the anode are erated protons (H + ) pass through an ion exchange separated. Potential [V] 1 1 anode : 2Cl– 2 cathode : 1/2O2 + 2H+ + 2e– (ODC) Cl2 + 2e– +1. 1 shows a schematic diagram of an elec- the Cl2. 2 Electrode potentials in HCl electrolysis SUMITOMO KAGAKU 2010-II 2HCl + 2NOHSO4 → 2NOCl + 2H2SO4 (3) 2NOCl → 2NO + Cl2 (4) 2NO + O2 → 2NO2 (5) NO2 + 2HCl → NO+Cl2 + H2O (6) NO + NO2 + 2H2SO4 → 2NOHSO4 + H2O (7) 4HCl + O2 → 2Cl2 + 2H2O (8) Since the process is complicated and there is much equipment that uses expensive materials. Cl2 is obtained from the sis process.2) The HCl start- 2. Electrolysis process for aqueous hydrochloric started operating a commercial plant capable of produc- acid ing 215.3) After operating a 20. After the Cl2 and ode (ODC). 1 ODC Cl2 Cl2 2e– 2Cl– 2H+ HCl anode aqueous hydrochloric acid and HCl gas electrolysis gen oxides as the catalyst and sulfuric acid as the circu- Comparison of HCl electrolysis lation medium. and Fig.36 +1. UhdeNora (joint venture between control the wetness and temperature of the membrane. and after the forma- The DuPont process makes use of a Nafion ion ex- tion of a 22% aqueous solution of hydrochloric acid. and HCl from the electrolyzer is recycled to the electrolysis gas supplied to the anode chamber is oxidized by the process after adjusting its concentration. commercialization in the 1960s it is being operated in multiple plants throughout the world.4) An ion exchange membrane covered with anode and H2 from the cathode. While technical improvements are being made to the anode Cl2 membrane cathode H2 Cl2 2e– 2Cl– H2 H+ 2e– HCl HCl processes described above. but there has plant at its Brunsbüttel plant in Germany in 2003. Oxidizing agent circulation methods The Kel-Chlor process developed by Kellogg can be H 2O mentioned.000 tons of chlorine per year at a TDI and MDI This method is called the Uhde process. obtaining the Cl2 product.23 H2O 2 Δ ≈ 1volt 3 2H+ + 2e– H2 0 3 Current density Fig. 2 presents a comparison of the Cl2 is obtained. construction 2 . Bayer. The unreacted HCl is recycled to the electrolysis voltage with the conventional method. it is change membrane and is known as a HCl gas electroly- sent to the anode and cathode.

4. A 30. Cl2 is obtained with scale. the catalyst (Fig. Inc. and the reaction takes place 100 0MPaG 0. 2HCl + catalyst 1 Cl2 + H2O + 59kJ/mol O2 2 1st 2nd Reactor Chlorinator Reactor Oxidizer (9) Using a copper chloride-potassium chloride-rare CuCl CuO 340 – 400°C 180 – 200°C CuO CuCl O2. 3. The reaction temperature in the fluidized bed reactor is 350 to 400°C. itomo Chemical developed a fixed bed process. which will be described CuCl2 catalyst in 1868. and is currently commercially operating activity than conventional catalysts and a sufficient re- at 60. have reported a two-stage fluidized bed system that uses a Deacon catalyst. obtaining Cl2 and CuO.) developed the MT-Chlor process. 3 to which alkali metal chloride and a rare earth chlo- Scheme of circulating dual fluidized-bed reactor ride are added. HCl.000 ton per year commercial production facility was operated in the 1970s. therefore.10) Toatsu Chemicals made it commercially viable at its Since the RuO2/TiO2 (rutile) catalyst has a higher Omuta plant. Cl2. O2 Fig. H2O with no side reactions. but it is said that The Sumitomo Chemical Chlorine Production Process it was stopped shortly thereafter. Catalytic oxidation of HCl gas Chlor process. In the first reactor (oxidizer). O2. Shell developed a fluidized bed air oxidation process capable of reactions at lower temperatures in 1960. generating a molten salt in reaction conditions. (currently Mitsui Aiming at an environmentally friendly process.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride costs are high. 7) This catalyst system achieves a high catalytic performance by using CuCl2 HCl. CuCl is oxidized at 360 to 400°C in the presence of HCl and oxygen. Mortensen et al. action rate can be obtained even at low temperatures Under the conditions of the reaction. the MTSince the discovery of the Deacon process 6) using a Sumitomo Chemical process. the chromia active species maintains its state as an oxide and the stability of the catalyst is greatly improved. which was discovered in Japan. In 1988 Mitsui TiO2 catalyst. Sum- Chemicals.9) A flow scheme is shown in Fig. This CuO is fed to the second reactor (chlorinator). 4 300 350 400 450 500 Reaction temperature (°C) Equilibrium conversion curves for HCl oxidation reaction as a function of reaction temperature 3 . 4) that are superior in terms of equilibrium for the using only the oxidation-reduction reaction without going through the chloride-oxide reaction cycle of the Deacon system. H2O earth compound/SiO2 catalyst. Inc. which was an improvement on the Deacon catalyst. Therefore. uses a RuO2/rutile-type oxygen that uses a Cr2O3 · SiO2 catalyst. there have been many reports of in the following. and CuCl produced by absorbing/ SUMITOMO KAGAKU 2010-II Equilibrium conversion for HCl oxidation (%) operates without melting. are the processes that are currently improved catalysts and articles on processes for cat- being operated commercially. and the conversion rate for HCl is 75% or more in one pass. Reaction equation (9) shows the reaction for producing chlorine using catalytic oxidation. DuPont started operation of a 200. both fluidized beds. Cl2.5MPaG 95 90 HCl/O2 = 4 85 80 75 70 65 60 250 Fig. and the Among these catalytic oxidation methods. which which is a fluidized bed process for oxidation with pure as a catalytic oxidation method.000 tons per year. Mitsui Toatsu Chemicals.8) Though not reaching commercial viability. but it is not operating at present. it is said to be suitable for reacting the unreacted HCl on the CuO at a relatively large-scale plants that can benefit from economy of low temperature of 180 to 200°C.000 ton per about 100% yield by circulating the catalyst through year plant in 1974. alytic oxidation.

5 shows the results of screening for catalysts. RuO2 particles on a is a lower intensity than a standard RuO2 sample with a nanometer order similar to that of normal supported sufficiently large crystallite. In (a) addition. Ru and Os. RuO2/TiO2 (rutile). By combining the SUMITOMO KAGAKU 2010-II 4 . Mn and Ni. 6 shows a TEM image of the RuO2/TiO2 cata- R2 and Ru-O can be found. The intensity of these peaks lyst.3 × 0. The coordination number catalyst are observed (Fig. as it has a high thermal stability as a main feature. 7 The crystallite size of this thin layer of RuO2 was an0. Ir. izontal. Conventional catalyst Pt/TiO2(anatase) Pd/TiO2(anatase) Rh/TiO2(anatase) Ir/TiO2(anatase) Os/TiO2(anatase) Ru/TiO2(anatase) RuO2/Al2O3 RuO2/SiO2 RuO2/TiO2(anatase) RuO2/TiO2(rutile) RuO2 Fig. Only Shell 11) has reported investigations on the use of noble metals. Furthermore. hereinafter abbreviated to Ru-Ru1). 6 showed specific activity as noble metal catalysts.9 nm Fig.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride reaction in equation (9). suggesting that RuO2 is present tile TiO2. The RuO2/TiO2 (rutile) catalyst has a unique struc- 0. 8. a thin RuO2 layer of nanome- Ru2 and carried out a simulation that approximated a ter order could be found supported on the TiO2 pri- rectangular solid with the a and b axes vertical and hor- mary particle surface as in Fig. Fe. but the Ru metal catalysts Fig. 6 (b)). Ru- Fig. 9 shows the Fourier transform spectrum for cover the surface of the rutile titania. hereinafter abbreviated to Ru-R2) (1) Structure of RuO2/TiO2 (rutile) catalyst and 6 O atoms (atomic distance = 0. in very fine crystals. and peaks belonging to Ru-R1.19 nm [2 atoms].35 nm. With RuO2 on anatase TiO2. As shown in Fig. they are not (Fig.20 nm [4 atoms]. 5 FE-STEM image of RuO2/rutile-TiO2 catalyst 12) Relative activities of the HCl oxidation catalysts alyzed from the EXAFS Fourier transform spectrum. hereinafter abbreviated to Ru-O). ture in which RuO2 crystallites with a size of 0. 6 (a)). and one Ru atom is surrounded by 2 nearest neighbor Ru atoms (atomic distance = 0. but with RuO2 on ru- for Ru in RuO2 is low. In- TEM images of RuO2/TiO2 catalysts 12) (a) RuO2/anatase-TiO2 catalyst (b) RuO2/rutile-TiO2 catalyst creased activity of approximately 50 times that of conventional catalysts was observed by changing the active species from metallic Ru to RuO2 and the TiO2 carrier to the rutile phase. Analyzing the EXAFS oscillation. and the c-axis as the height. RuO2 has a rutile structure. the conversion ratio is high.5 0 1 Relative activity Fig. long life RuO2/TiO2 (rutile) catalyst. 1. Fig. Use of highly active RuO2 / TiO2 (rutile) catalyst The Sumitomo Chemical process uses a highly RuO2 active.31 nm. but those catalysts were obtained by building up the results of investigations focusing on the reactivity of the outermost d electrons of noble metals such as Pt. when the RuO2/TiO2 (rutile) catalyst we found the coordination numbers for Ru-Ru1 and Ru- was studied by FE-STEM. Research (b) on catalysts for O2 oxidation of HCl has mainly focused on the field of base metals such as Cu. it makes possible a long-term continuous operation of the fixed bed reactor. Cr. Rh. 8 next nearest neighbor Ru atoms (atomic distance = 0. 7.

an industrial cata- –3 Fourier transform k3x(k)/nm The strong interaction between metallic Ru and TiO2 RuO2 standard(ca. the high thermal stability can be thought of as being due to the strong interaction between RuO2 and TiO2.35nm a Fig. in high yields. 10 Ball model of RuO2/rutile TiO2 catalyst surface 12) c b to the specific structure of the RuO2 and the rutile TiO2. heat transfer salt (HTS) is circulated to SUMITOMO KAGAKU 2010-II 5 . but the interaction Ru–Ru2 between RuO2 and TiO2 has also been described 14). 10. 11. An example of the cell of the RuO2 crystallite.5 times that of the catalyst initially developed by making various im- coordination numbers obtained. This catalyst provides both the catalytic activity and To use the entire catalyst layer effectively. ble to produce Cl2 with a higher purity than electrolysis This 0. On the shell side activity is the high level of dispersion of the RuO2 due of each zone. we estimated the size provements in its physical properties. of the RuO2 crystallite to be 0. at low cost. crystallite covered an estimated 90% of the TiO2 surface from the relationship between the specific surface area for TiO2 and the support quantity of RuO2.31nm Ti c b 0. as in Fig. 8 RuO2 crystal 12) In addition. the reactor life to satisfy the performance needs of an industrial cat- is divided into multiple zones. and Cl2 and water are obtained by a gas (2) Industrial catalyst phase reaction using the RuO2/TiO2 (rutile) catalyst. in the development of the industrial catalyst. we were able to increase the thermal conductivity of the catalyst up to approximately 1.9 nm. In this way it is possi- surface of the rutile TiO2 primary particles. 30 has been thoroughly reported13). Overview of the process we concluded that the RuO2/TiO2 (rutile) catalyst has a One key feature of the Sumitomo Chemical process structure in which ultra-fine crystallites of RuO2 with is achieving a compact fixed bed reactor by developing dimensions of approximately 0. long-life catalyst.3 nm corresponds to the thickness of one unit of salt.3 × 0.6 Distance/nm Fig. then controlling the tem- alyst. Putting it another way.9 nm cover the a highly active. 2. From the results of FE-STEM and EXAFS analysis. 9 Fourier transforms of the EXAFS spectra of (a) RuO2 standard and (b) RuO2/rutileTiO2 catalyst 12) required in order to efficiently eliminate the reaction heat generated in the oxidation reaction of HCl and pure O2. According to the latter.25nm) RuO2/rutileTiO2 0 lyst for a fixed bed reactor high thermal conductivity is 0 0. 10 In addition to improve the activity and thermal stability of the catalyst as discussed above.2 0. (1) Oxidation reaction step HCl and oxygen are supplied to a multitubular fixed bed reactor.3 × 0.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride Ru O O Ru 0. when a complex oxide of RuO 2 Ru–O 20 and TiO2 is formed. The main reason it shows a high level of catalytic perature independently in each zone. RuO2 process is shown in Fig. a Ball model showing a bulk Fig. the sublimation of the Ru compoRu–Ru1 nent in the high-temperature reaction is limited to 1/40 of corresponding non-supported RuO2. Therefore.4 0.

Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride Oxidation HCl Absorption Drying Cl2 Purification Cl2 Recycle oxygen Purge H2SO4(Conc. Since the previous oxidation reaction is carried out at Fig. and there were no prob- When higher Cl2 yields would be desired. Demonstration of catalyst performance and HCl Recovery process Dewatering The 1000 ton per year demonstration plant shown in Fig. 12 was constructed. which contains Cl2. is next sent to a drying step. 11 An example of HCl oxidation process flow 12) Fig. It may As shown in Fig. it is possible to recover almost all feed HCl as Cl2. and it is furic acid.O2) dried by bringing it into contact with concentrated sulfrom the bottom of the column.O2) 100 and only water is removed at the top of the column. making it possible to adjust to the target reaction temperature.) (4) Chlorine purification step The Cl2 is liquefied by compressing and cooling the dry gas from the drying step. eliminate the reaction heat. highly pure Cl2 is obtained by distilling and eliminating the impurities HTS present in the solution. HCl can be lems with respect to corrosion resistance and durabil- separated from the hydrochloric acid by distillation at ity of the equipment and materials or with operability. and the unreacted HCl is absorbed in water and separated from the bottom of the column as hydrochloric acid. By 90 returning the liquid in the column to the process. which is mainly composed of Cl2 and O2. (2) HCl absorption step The reaction gas is quenched.HCl.15) HTS (Return) (3) Drying step The water containing gas obtained in the HCl absorp- SUMITOMO KAGAKU 2010-II Target 85% 70 60 50 0 5000 10000 15000 Operating time (h) Product (Cl2. the hydrochloric acid obtained from the bottom of the column is not contaminated by sublimation of the catalyst component. the liquid from the distillation column is Feed(HCl. it was possible to maintain the easily be commercialized as hydrochloric acid pro- HCl conversion ratio at the targeted 85% for two years duced as a byproduct. The eliminated heat is recovered as steam by a heat recovery boiler and is used effectively in the process. part of it is purged to a caustic scrubber. Furthermore. of demonstration operations.H2O. Hydrochloric Acid HCl 3. 12 HCl oxidation demonstration pilot plant 12) a comparatively low temperature. The gas obtained at the top of the column. For cases in which further increased Cl2 yields would be required. Sulfuric acid that contains water is obtained HCl conv. and the performance of the RuO2/TiO2 (rutile) catalyst and overall process was confirmed. Most of the uncondensed gas HTS H2SO4 (Waste) Option Recycle HCl O2 containing O2 is recycled to the reaction process. O2 H2O and inert components. distilled in a vacuum Fig. 13. (%) supplied to a dewatering column. 13 HCl conversion as a function of time in operation in the demonstration reactor 12) 6 . Equilibrium conversion 80 HTS tion process is supplied to a drying column. and to prevent accumulation of substances such as inert components. increased pressure. and then recycled to the reaction.

2 sintering by highly dispersing the active species. As a result of examining various types of blocking ad- Typically. we thought that we might be able to con- the target without trouble.D. Rough- in the cr ystals vaporize and are again absorbed by ness can be seen on the TiO2 surface in (b) while the other crystallites. there are the methods of adding Component Sumitomo HCl oxidation (%) Cl2 99. It can be seen that the thick- teraction and a high level of thermal stability as was ness of the RuO 2 cr ystal layer exposed to the TiO 2 discussed previously.90 99. SUMITOMO KAGAKU 2010-II 7 . the sintering blocking material must be supported at a nanometer level to control nano-order 4.16) – 18) Considering the fact that the TiO2 surface presents a smooth image as shown in (a). for preventing the sintering of the carrier. 20) and stabilized zirconia 21) that adds Y to ZrO 2 . Fig.20).1 O2 0. carrier surface as in Fig. it was li- lyst to prevent Pd sintering.000 tons reaction for HCl. We can mechanism was two-dimensional as in the above 1) presume that this RuO 2 sintering is related to and 2).6 N2 0.1 for example co-impregnation of a mixed aqueous solu- Electrolysis (%) La2O3 and CeO2 to γ-Al2O319). 16 shows a SEM image of (a) the TiO2 in the crystals move on the carrier and are absorbed by surface. as H2 N. Catalyst improvement technology (1) Development Concept RuO2 sintering. we found that a catalyst for the sintering of suppor ted metals: 1) The case where nano-order SiO2 and RuO2 were supported on where the crystallites themselves migrate on the car- the TiO2 surface showed a strong effect in sintering rier collide and aggregate. phere. 15. but the catalyst life reached Therefore. For example. be carefully selected taking into account the chemical and has since then been licensed to several companies stability and thermal stability in the reaction atmos- in Japan and overseas. 0. the Cl2 ob- trol the RuO2 sintering by adding particles of a size hav- tained from the demonstration plant had higher purity ing the same par ticle diameter as the RuO 2 on the than chlorine from electrolysis as shown in Table 1. or the method of adding CeO2 and MgO to a Pd/Al2O3 cataAfter the demonstration of this technology. the sintering blocking material must per year that continues its operation to the present day.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride Fig. deactivation of the catalyst. 2) the case where the atoms prevention. 3) the case where the constituents after 5 minutes of exposure to an electron beam. Others methods prevent tion of Zr. (b) RuO2/SiO2/TiO2 catalyst and (c) image (b) other crystallites. starting operation of around 100. 15 Fig. 14 FE-STEM image of the used catalyst after two years of operation 12) Table 1 Comparison of the quality of chlorine obtained by Sumitomo HCl oxidation and by electrolysis of sodium chloride 12) TiO2 Conceptual model of the preventing RuO2 of sintering on the RuO2/TiO2 catalyst surface (2) Development of improved catalyst Several examples have been reported on adding a third component to a catalyst for the purpose of preventing sintering. 14 shows an FE-STEM Z contrast image of the cat- RuO2 and TiO2 in this catalyst system have a strong in- alyst used for two years. we can consider the following three cases ditives and addition methods. Sintering blocking material RuO2 TiO2 Fig. Furthermore.08 0. In addition.01 0. we assumed that the sintering carrier surface increased because of sintering. 23) censed amongst others to a domestic chemical pro- Since highly corrosive gas is present in the oxidation ducer in 2002. Hf and Ti compounds and RuCl3 22).

(6) construction costs are low because the 6 various pieces of equipment. c-axis).b-axes. The 2 Bayer-DeNora process reduces the electricity con1 sumed by about 30% over the conventional electrolysis 0 0 8000 16000 Operating time (h) Fig.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride The RuO 2 is reduced if it is exposed to an electron system with an electron microscope. and we can assume that the Sumitomo Chemical process will produce Cl 2 at a lower cost. version ratio is high because of the use of a fixed bed Since it was difficult to observe the RuO2 in this catalyst reactor. and 15nm in addition. a. c-axis). opening the possibility for highly competiFig. we analyzed the beam for 5 minutes in the field of view in (b). maintained. beginning with the reac5 tor.b-axes. SUMITOMO KAGAKU 2010-II process by using an oxygen depolarized cathode. Economics Sumitomo Chemical has not only been able to carry (3) Evaluation of the improved catalyst thermal sta- out continuous operation using the long-life catalyst and highly reliable process for two years. (2) the one-pass con- carried out with and without the addition of SiO 2 . 16 surface 12) SEM images of catalyst (a) TiO2 surface (b) RuO2/SiO2/TiO2 surface (c) RuO2/SiO2/TiO2 surface after irradiation of electrons for 5 minutes tive catalysts that are not as easily affected by the variations in price typical of noble metals. Even so. Considering the fact that the sintering prevention effect was found with this reaction system with the SiO2 (a) (b) on the same order as the RuO2. thus allowing us to reduce the amount of Ru used. RuO2/SiO2/TiO2 (◆ . but the system with the added SiO 2 roughness seen in the image in (b) is seen mainly as (RuO2/SiO2/TiO2) had a stable RuO2 crystallite diame- SiO2. makes the process energetically efficient. 17 shows the changes over time in the RuO2 this process to be superior economically. The RuO2 crystallite diameter was in between the bumps of the rough surface. (3) Cl2 is obtained with a high yield because almost all of the unreacted hydrochloric acid is recov- Crystallite size of RuO2 (nm) ered. The reasons crystallite with the same spatial velocity and same con- are: (1) the catalyst costs are reduced because of the version conditions when the reaction of HCl and O2 was highly active. 15. (5) the recovery of the reaction 7 heat in steam. . 17 RuO2 crystallite size as a function of time in operation under HCl oxidation reaction 12) RuO2/TiO2 ( . ter for 1000 hours after the star t of the reaction. since the CO2 emissions are low because of the decreased power 8 . we could presume that the the reaction. 4 Table 2 compares unit consumption of the Sumitomo 3 Chemical process and the Bayer-DeNora process. corresponding to a catalyst very close to the concept confirming that the nano-order crystallite diameter was model in Fig. long-life catalyst. we can assume that the (c) sintering mechanism is mainly the migration of the crystallites themselves. and high quality Cl2 is obtained. but has also found bility Fig. there is a large difference in the unit consumption of electricity. In addition. (4) the electric power consumption is a fraction 8 of that for electrolysis. the same with or without the addition of SiO2 before From these results. ■ . 24) which is a hydrochloric acid electrolysis process. The improved catalyst that was developed prevents RuO2 sintering and maintains a high level of activity. a. and it can EXAFS Fourier transform spectrum and calculated the be seen that nano-order metallic Ru particles appeared crystallite diameter. are compact. depending on the site conditions. and RuO2 is present in the spaces in between.

(2001). Sci. 24) J. According to Crihan et al. Guimaraes and L. Soc. Seki. W. Asia. Pulvermacher. there are steps for which the main points are re-bonding with Cl2 and re-adsorption of O2 after the chlorination of RuO 2 .. 2131 (2008). K. Catal.03 O2 (Nm3) 163 159 Power (kwh) 165 1100 2) Uhde’s brochure. Knapp. 7-116516 (1995). J. presumed that the state where the bridging O in RuO2 13) S. Benson. highly regarded not only because it makes it possible to 21) W. Yoshida and H. Seki. Motupally.. 224 (1973). J. Oblad. recycle the HCl produced as a byproduct. Freire and J. Mortensen. J. used in situ surface x-ray diffraction analy- 17) P. preventing global warming. 5) A. T.. 23 (1969). Am. Shokubai. August 26-30.. C. 47. Hofmann. Sci. W. 16) E.. 390 (1974). Zweidinger. Mori. 54. 8) T.H. M. 212. 33 consumption. US patent 5411641 (1995). 7 (3). Chem. 31 (2). 20) T. 15 (1991). United ogy. Catal. petitive chlorine production process. it is 12) K. Lundgren. 116 (1989).Ramírez. 1) S. 26) In addition. highly reliable. Tauster et al. Chem. Dieguez. A. D. M. K. Crihan. Seitsonen and worldwide contribution with this as a technology for H... Catal. 64 (1). Schmal. Am. Lund- Pérez. Suzuta. Mah. Soc. 4) E. further improve both catalyst and process.. 272. Over. 14) Johnson Matthey. G.27) The Sumitomo Chemical HCl oxidation technology is (2001).49.Chem. GB patent 1403 (1868). 29 (2008). Shokubai. R. Int. Zwei- (1978). Electrochem. F. 9) M. References 27) S. they concluded that the high chemical stability of RuO2 under high-temperature HCl and the gradual sintering activity were factors in the high performance of RuO2/TiO2.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride Table 2 Comparison of unit consumption between Sumitomo HCl oxidation method and Bayer-DeNora electrolysis method 12) Unit consumption (Units/T-Chlorine) Sumitomo HCl oxidation Bayer-DeNora electrolysis HCl (Ton) 1. T. the plants that have been licensed up to now are operating without problems. Rhodes. N. C. 2131 (1999). Royal Soc. JP patent. T. Weidner. Over. H. Chicago. Yamanaka and J. GB patent 1046313 (1966). López. 15) Sumitomo Chemical Company Limited. J. and the catalyst and process are States. Deacon. Appl.Eng. Weststrate. J. Interface. “Modern chlor-alkali technology. 29. T.. T. Ozawa and M.. In addition. Surv. J. US Patent 3945948 (1976). with a low impact on the environment. Cambridge (2001). A: General. US patent 3210158 (1965). Nakada. SUMITOMO KAGAKU. J. Conclusion 2004-!. Kimura. Minet. IL. E. Mater. S. 291 (1990).Soc. making it an extremely com- (1). Nishida. Y. Chemical Eng. we would like to 25) D. 169 (2010). 3) Bayer News release. K. ogy than salt and hydrochloric acid electrolysis technol- 222nd ACS National Meeting. 1 (2004). A. L. 170 is substituted with Cl in the HCl oxidation reaction (RuOxCly) is a stable activated state.Cer. J. sis and analyzed the RuO2/TiO2 in the HCl oxidation 18) C. more resource conserving and energy efficient technol- 23) M. it is superior in terms of measures against global warming. September (2009). Catal. J. gren and H. I. P. 26) N. T. Marín and J. Angew. 9 (3). 19) M.05 1. In the coming future. 32 (1998). 34. Kiyoura. SUMITOMO KAGAKU 2010-II 9 . Catal. Catal. Hibi. dinger et al. but also as a 22) Idemitsu Kosan. J. Issoh. from density functional theory (DFT) and experimental data. Ed. Zweidinger. J. Gómez-Segura. O. 14. T. 10) K. 19 (1981). as a result. Koezuka. JP patent 4182608 (2008). 7) Shell Oil Company. Ind. there have been several reports giving examples of research on RuO2/TiO2 (rutile) in a HCl oxi- 11) Shell International Research Maatschappij. Andersen. 100. Wanke. Iwanaga. dizing atmosphere.. Hayata. p. 61 (7). Lett. R. Ruckenstein and B. Chem. Flynn and S.25) According to López et al. Recently. 17 atmosphere. 168 (2010). G.. Furuya. S. Bartholomew. Moorhouse. Chlorine and hydrogen from hydrochloric acid by electrolysis (1990). 6) H. Balmes.P. and make a C. E. J. Du Pont de Nemours and Company.. 8”. Abe. Tsotsis and S. P. 255. J. E.

Ltd.. Ltd. Ltd. Process & Production Technology Center Researcher Kohei SEKI Masahiro KINOSHITA Sumitomo Chemical Co..... Basic Chemicals Research Laboratory Senior researcher. Basic Chemicals Research Laboratory Researcher Sumitomo Chemical Co. Ltd. Ltd. Basic Chemicals Research Laboratory Senior researcher Sumitomo Chemical Co.Trends and Views in the Development of Technologies for Chlorine Production from Hydrogen Chloride PROFILE Hiroyuki ANDO Carlos KNAPP Sumitomo Chemical Co. PhD in Chemistry Presenet post: Organic Synthesis Research Laboratory Youhei UCHIDA Norihito OMOTO Sumitomo Chemical Co. Basic Chemicals Research Laboratory Senior researcher Sumitomo Chemical Co.. Process & Production Technology Center Senior researcher SUMITOMO KAGAKU 2010-II 10 . Ltd.