Chemical and Petroleum Engineering, Vol. 47, Nos. 56, September, 2011 (Russian Original Nos.

56, MayJune, 2011)

OPTIMIZATION OF TEMPERATURE REGIME FOR AN INDUSTRIAL CLAUS REACTOR

Yu. V. Vasiliev, O. I. Platonov, and L. Sh. Tsemekhman

On the example of modernizing an SRU catalytic reactor of the elemental sulfur production workshop of the Copper Plant of Norilsk Nikel Mining and Metallurgical Company, the possibility is demonstrated of temperature regime optimization for a Claus industrial reactor. Data are presented for two years of inspection before and after catalytic reactor modernization, indicating that due to a change in the scheme for introducing processing gas there is a reduction by an order of magnitude of the temperature gradient within the catalytic reactor and an almost twofold reduction in its overall gas dynamic resistance.

Catalytic reactors of numerous units for preparation of sulfur by the Claus method (SRU) [1] operate in the presence of elemental sulfur, entering with process gas, which governs the ineffective characteristics of their operation. Operating temperature regimes for these SRU reactors (Claus reactors) are 220269C, which corresponds to the range of an anomalously high liquid sulfur viscosity [1]. This sulfur is held in capillary slots between catalyst grains and accumulates close to them, forming stagnant zones for the gas flow, where diffusion mass transfer of the flow with grains slows down [2]. As a result of this in the catalytic layer of a Claus reactor there is formation of local areas with reduced throughput, which leads to nonuniform temperature distribution within a reactor, and also reduces the average efficiency of the catalytic layer and overall efficiency of a Claus reactor, increasing its gas dynamic resistance. The possibility is demonstrated on the example of an SRU catalytic reactor of the elemental sulfur production workshop (ESPW) of the Copper Plant (MZ) of Norilsk Nikel Mining and Metallurgical Company (GMK NN) of optimizing the temperature regime, i.e., reducing temperature gradients within the industrial Claus reactor due to changing the scheme for introducing process gas. Catalytic reactors of the ESPW MZ GMK NN that are intended for conversion of sulfur-containing components of process gas into elemental sulfur are traditional equipment of the shelf type, made in the form of horizontal internally lined cylinders 5600 mm in diameter and 13 m long. In the central part of the equipment on a horizontal grid there is a stationary layer of catalyst 1300 mm thick (Fig. 1a). In order to introduce process gas into the reactor (reduced sulfur dioxide), the design includes three vertical branch pipes 800 mm in diameter with diffusers, located at the top in the diametral plane of the reactor. Removal of gas is accomplished through two branch pipes cut in the bottom of the reactor. Due to closeness to the catalytic layer surface, the stream of process gas emerging from the lower sections of inlet branch pipes it is pushed into the catalytic layer at a distance of ~2.5 gauges, i.e., without sufficient exposure, which governs the nonisothermal nature of the catalytic layer in ESPW planned converters. With a width of catalytic layer of more than 5 m, this governs formation within it of stagnant zones, and as a consequence nonuniform heating of the catalytic layer, developing significant temperature gradients. The nonisothermal nature of the catalytic layer reflects the low efficiency of using the volume of catalyst and the increase in gas dynamic resistance of the planned ESPW reactor. Gipronikel Institute, St. Petersburg, Russia. Translated from Khimicheskoe i Neftegazovoe Mashinostroenie, No. 5, pp. 1113, May, 2011. 0009-2355/11/0506-0305 2011 Springer Science+Business Media, Inc. 305

Fig. 1. Diagram (diametral section) of catalytic converter R-1-I of the ESPW MZ GMK NN: a) originally planned version; b) after modernization; direction of processing gas inlet-outlet indicated by arrows; points (14) are locations of thermocouples in catalyst layer.

Insufficiently effective use of the catalyst in the planned ESPW reactor appears as a strong temperature dependence of gas dynamic resistance for the Claus reactor, shown in Fig. 2. The various symbols, corresponding to different periods of inspection of two identical ESPW reactors, demonstrate measured valued values of catalytic layer resistance p, standardized for a square of process gas input F through the reactor: R = p/F2. Clear circles show values of standardized resistance R of converter R-1-I, operating within the composition of the first ESPW production line, and shaded symbols (crosses, black point and triangles) show values of R for an identical converter R-1-II of production line No. 2. The clear rhombus in Fig. 2 shows the average value of gas dynamic resistance R of reactor R-1-I after modernization, described below; horizontal and vertical sections show the dispersion of empirical average values of temperature t and resistance R, Other large symbols, i.e., triangles and squares (their size corresponds to argument and function dispersion) show the average values of gas dynamic resistance in modernized reactor R-1-I for individual examination periods. All these measurements were made when in the planned ESPW reactors an aluminum oxide catalyst DR from the firm Rhone-Poulenc was used, represented by spherical granules 56 mm in diameter. The nature of static relationship R(t) is revealed: gas dynamic resistance of a catalyst layer in a reactor as a whole decrease with an increase in temperature (see Fig. 2), i.e., it corresponds to formation in relatively cold zones of a reactor of viscous sulfur deposits, filling intergranular spaces, but removed with an increase in temperature. The empirical relationship R(t), corresponds qualitatively to known ideas [2], and assumes temperature nonuniformity oft the catalytic layer as a result of cooling of stagnant zones at its periphery, primarily at the ends of a reactor. Presence of significant temperature gradients within the catalytic layer of reactor R-1-I is directly confirmed by data provided in Table 1 for measurements of temperature with the reactor by means of four thermocouples, uniformly buried in the catalyst layer through the side walls of the reactor at points 14 (see Fig. 1). In order to overcome stagnant zones in the catalytic layer, another scheme was developed for input and output of process gas for catalytic reactor R-1-I, i.e., through branch pipes placed in the end wall of the reactor in order that the stream of process gas spreads over the surface of the catalytic layer. With sufficient length of a stream, comparable with the length of the reactor, washing by the flowing gas of the catalyst layer surface provides quite uniform heating, minimizing temperature gradients in the layer. Modernization of the catalytic reactor of ESPW production line No. 1, carried out in the major overhaul period of the line in 2000, included construction of horizontal branch pipes for the input and removal of process gas, located perpendicular to the end wall of the equipment (see Fig. 1b). The diameter of the inlet branch pipe was calculated for an empirical isothermal model of a heated stream [3] from conditions for achieving an actual axial stream for the opposite end wall of the 306

Fig. 2. Values of gas dynamic resistance R = p/F 2 in relation to temperature t: ESPW planned reactors: R-1-I (1), R-1-II (2); modernized reactor R-1-I (3). Catalyst DR (56 mm). Inspection periods: 03.2211.20.2001 (c), 02.0706.21.2002 (d); 07.2808.14.2003 (b). For the rest of labeling see text.

reactor. The width of this wall (reactor diameter) exceeds by a factor of six the initial gauge of this stream, and therefore in order to prevent formation close to it of zones with reverse gas flow circulation (turbulence) two subsidiary inlet branch pipes of smaller diameter were proposed. The planned vertical inlet and outlet branch pipes for process gas were removed during overhaul and their openings were plugged. Temperature regimes for reactor R-1-I operation of the ESPW production line No. 1 before and after modernization, established according to these inspections during industrial operation, are compared in Table 1, where bold face shows the average of a selection of 80 temperature values in the catalytic layer of ESPW R-1-I, recorded in the examination period from 02.25.1999 to 06.02.1999. For comparison, results are provided in normal face for temperature measurement in the same reactor with a change in the process gas inlet and outlet. It may be seen from the data in Table 1 that in the planned reactor the temperature drop over the catalyst layer reached on average ~30C, but after modernization (in the same catalyst) it was reduced by an order of magnitude. Even current values of temperature, subject to dynamic variability, differ less in the modernized reactor than average values of temperature in the catalytic layer of the planned reactor R-1-I. This tendency was also unchanged after replacement of catalyst in August 2003, i.e., the temperature drop, measured by thermocouples, even for current values in the modernized reactor is markedly less than for average data for planned reactor R-1-I of the ESPW MZ GMK NN. A significant reduction in the temperature gradient within the catalytic reactor after its modernization is also confirmed by a collection of separate current temperature values for 03.2223.2001. Simultaneously with a reduction in the temperature gradient within the catalytic reactor R-1-I after modernization of the process gas inlet assembly the overall gas dynamic resistance of the reactor was reduced by almost a half. This is indicated both by the average values of gas dynamic resistance for reactor R-1-I for two years after modernization, shown by a rhombus in Fig. 2, and also the average resistance for the range of temperature values in the modernized reactor for separate inspection periods, shown by other large symbols (squares and triangles). 307

TABLE 1. Temperature Values for Four Points of a Catalyst Layer for Planned Converter R-1-I of the ESPW MZ GMK NN (bold face) and after Its Modernization
Values of temperature at points, C Catalyst Inspection period 1 2 3 4

DR (56 mm)

02.25.9906.02.2000*
**

220 285* 324** 215 269 257 302 306 352 341 340 298

234 282* 318** 212 283 258 296 299 345 336 327 307

187 253* 318** 214 279 260 311 317 349 334 350 307

207 258* 322** 215 279 260 310 316 348 338 297 298

08.29.2005 09.03.2005 CR-3S (36 mm) + CRS-31 09.04.2005 09.06.2005 (at 19:00) 09.06.2005 (at 21:30) 09.15.2006 09.21.2006 CRS-31 + CR-3S (36 mm) 09.26.2006 09.27.2009
* **

Average for 05.20.1999; 08.24.1999; 08.26.1999; 09.29.1999; 10.07.1999; 03.20.2000; 03.30.2000; 03.31.2000; 05.11.2000; 05.24.2000. Average for measurements at: 18:00 and 22:00, 03.22.2001; 2:00, 6:00, 10:00, 14:00, 18:00, 03.23.2001.

Thus, a change in the inlet and outlet scheme for process gas in catalytic reactor R-1-I of the ESPW MZ GMK NN made it possible to improve considerably its operating properties, reduce temperature gradients and decrease gas dynamic resistance for the catalytic layer in the Claus reactor as a whole. On the basis of the practical experience, a catalytic reactor was planned for SRU tailing gases of the workshop for cleaning coke gas of the Magnitogorsk Metallurgical Combine [4], and operated successfully since 2004.

REFERENCES 1. 2. 3. 4. V. R. Grunwald, Gaseous Sulfur Technology [in Russian], Khimiya, Moscow (1992). M. E. Aerov, A. M. Todes, and D. A. Narinskii, Equipment with a Stationary Granular Layer: Hydraulic and Thermal Bases of Operation [in Russian], Khimiya, LO, Leningrad (1979). RF Patent 2034633 MKI B 01 D 45/00; F 22B 31/02, Method for processing discharge dusty high-temperature gases and a device for accomplishing it, publ. 05.10.1995, Byull., No. 13. O. I. Platonov, A. G. Rabko, L. Sh. Tsemekhman, and D. A. Mironov, Catalytic treatment of Claus off gas as a part of coke gas desulfurization process, in: Sulphur 2005: Conf. Papers, British Sulphur Events, CRU Publishing Ltd., London (2005), pp. 167172.

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