VoL8 No.2 1999 Journal of Natural Gas Chemistry 1s A STUDY ON REMOVAL OF ORGANIC SULFUR COMPOUND WITH MODIFIED ACTIVATED CARBON FAN Hui-Ling LI Chun-Hu = GUO Han-Xian Institute of Chemical Engineering of Coal, Talyuan University of Technology Taiyuan, Shanxi 030024 ‘Abstract The effects of water vapor and temperature on the removal of organic sulfur compounds by modified activated carbon were studied in this paper. It was found that water vapor had a negative effect on the removal of carbon disulfide by the activated carbon impregnated with organic amine ‘The results of using activated carbon impregnated with K3COs for the removal of carbonyl sulfide in the temperature range of 30~60°C showed ‘that 40°C was a favorable temperature. Fixed-bed breakthrough curves for the adsorbent bed were also offered in this paper, Keywords modified activated carbon, carbon disulfide, carbonyl sulfide, removal Introduction Sulfur compounds exist in natural gas, petroleum and various raw gases made from coal, With high sulfur coal as the raw material, the lifetime of the ammonia synthesis catalyst is reduced greatly because of the high concentration of the sulfur compound in the synthesis gas, especially organic sulfur, such as CS2 and COS. Activated carbon has been employed as one of the main sorbents for desulfurization due to the high plentiful pore. However, low sulfur capacity and bad selectivity restrict its use in the field of purification, In recent years, modified activated carbon has attracted more and more attention since it ‘overcomes the defect of the common one, and is considered to be the most promising sorbent for the removal of sulfur compounds, but almost all published information concentrated on the removal of H2S, those on the removal of organic sulfur, especially CS) Received September 8, 1997, revised version received December 10, 1998152 Journal of Natural Gas Chemistry Vol.8 No.2 1999 is rather sparse. This paper reports the effect of water vapor on CS2 removal by the activated carbon impregnated with organic amine and the effect of temperature on COS removal on the KyCO3 modified activated carbon, Experimental Activated carbon preparation The granular activated carbon named E, D and B used in this study were manufactured by three plants in China, respectively. The chemicals used in this study are all A.R. grade. ‘The physical properties of these activated carbons are listed in Table 1 Table 1 Physical property of activated carbon Granular activated carbon E D B BET surface area /m>-g! 945.8 922.0 94.3 Bulk density / gmL"! 0519 0.453 0382 Pore volume / mL-g"! on 0.72 0.7 Particle size / mm x mm BS35 G3.0x30 35x35 ‘The three kinds of activated carbons were impregnated with a solution of organic amine or K2CO3 using incipient wetness technique. The saturated activated carbon was kept humid for 24 h at room temperature. The activated carbon impregnated with organic amine was dried at 70~90°C for 3 h, then the temperature was raised to 120~130°C and kept constantly for 7 h, while the activated carbon impregnated with K2CO3 was heated at 100~120°C, Samples E and D modified with organic amine were used for CS2 removal, and sample B modified with KyCO3 was used for carbonyl sulfide removal. Preparation of reactive gases In this study, a certain amount of carbon disulfide coming from the CS liquid was diluted with nitrogen to a certain concentration before it was used as the reactive gas. CS2 liquid was made in Tianjing Chemical Factory, the boiling point is 46°C. Carbonyl sulfide was prepared by the reaction of a saturated solution of potassium thiocyanate with the 50%(w1) sulfuric-acid at 30°C. After being purified, the COS was filled in gas cylinders made of glass fiber reinforced plastics with nitrogen as the balance gas.Fan, HLL, et al., Removal of Organie Sulfur Compound with Modified Activated Carbon 153 Apparatus and reaction conditions Desulfurization experiments were carried out under atmospheric pressure in a fixed- bed reactor system which is shown in Fig. Fig.1 Schematic diagram of apparatus for the experiment 1. Nitrogen 2. CS2*Nz or COS+Nz 3. Pressure regulator 4. Steadying flow valve 5, Micro-adjust_ 6. Flowmeter 7. Three-way valve 8, Soap bubble meter 9, Humidifier 10. Preheated snake tube 11, Water-thermostat 12. Sorbent bed 13. Water jacket 14. Reactor Fig. presents a schematic diagram of the experimental apparatus, The reactor was a lass tube of 14 mm ILD with a water-jacket outside, The water jacket was full of circulating water from water-thermostat which could control precisely the experimental temperature, The activated carbon was packed in the reactor of about 45 mm high. ‘The gas distribution system consisted of steadying flow valves, pressure regulators and flow meters, was arranged to control the flow rate and composition of the gas stream. The gas stream was a mixture of CS2 and N3 with a $ concentration of 138 mg/m? or a mixture of COS and Np with a $ concentration of 22 mg/m?, and it could be conveniently saturated with water vapor in a humidifier if necessary in the experiment. The temperature of the humidifier was kept constant at 25°C. Before entering the reactor, the gas stream ‘was preheated in the thermostat to the temperature as that of reactor. The sulfur concentrations of the gas stream in the inlet and outlet were analysed by a gas chromatograph with a FPD detector. TPD and GDX columns were selected for CS) and COS separation, respectively154 Journal of Natural Gas Chemistry Vol.8 No.2 1999 Results and discussion Experiments were carried out by adding water vapor to the gas stream to show the effect of water vapor on the removal of CS2 by the activated carbon modified with organic amine. 1d ‘a cy sy £8 os 28 os g8 £5 gs Be hee pas" BRP os 5 EO on = Bs &8 onl BS 02 a 0 MITTEE Yer Toth Toe “= with water vapor + without water vapor (a) E-CS, system (b) D-CS2 system Fig.2, Breakthrough curves for CS2 removal Fig.2 shows the fixed-bed breakthrough curves for E-CS2 and D-CS2 systems at 30°C and 2857 hr!. As we can see from this figure, water vapor which had a higher concentration (22.93 g/m?) than that of carbon disulfide had a remarkable negative effect fon carbon disulfide removal. The carbon disulfide removal capacity was reduced significantly when water vapor was added into the gas stream. Water vapor can greatly lead to the reduction of lifetime of breakthrough during removal of carbon disulfide, The higher the ratio of C/Co was, the more greatly the two breakthrough curves with and without water vapor differed. It is clear from the results that a competitive adsorption between carbon disulfide and water molecules existed on the activated carbon especially when water vapor was at a higher concentration. The explanation of the phenomena was given by Smithl'-3]. He reported that adsorbed oxygen, which always existed on the surface of the activated carbon, appeared to enhance the adsorption ability of polar molecule, such as H20. In other words, when water vapor contacted with the activated carbon, oxygen-legend was formed. The experiment results shown in Fig.2 were in agreement with that reported by N.Pechler and G,Emig(“], Same results were also obtained by L-Saletal®l, He observed that the relatively high content of moisture in the inlet gas could affect unfavorably the adsorption of sulfur compounds on the activated carbon. TheFan, HLL. ef al, Removal of Organic Sulfur Compound with Modified Activated Carbon 158 other reason for the negative effect of water may be that water film covers the outer- surface of the carbon, which could restrain the further migration of CS to the internal surface of the activated carbon. It was found that the reacted activated carbon was moist when it was taken out from the reactor. 10 ¢ 3 Ratio ut ont concentration of CS ool 0 ry 700) 750 00 ‘Teme min sme are aac Fig.3 Breakthrough curves of sample B for COS removal Fig.3 shows the breakthrough curves of sample B for COS removal at temperature of 30°C, 40°C and 60°C, respectively. In this plot, humidifier was kept at the temperature of 25°C. The space velocity for all the cases was 2 857 hr! The results in Fig.3 show that COS adsorption capacity strongly depended on ‘temperature, During the initial period of about 120 min of the experiment, the COS removal ability of the activated carbon increased with the increase of experimental temperature, but changed in the following time duing which COS removal ability decreased rather sharply with time at 60°C than that at 40°C which maintained a relatively steady: state. As a result, the operation condition plays an important role for effective utilization of the activated carbon. The optimum temperature for the utilization of modified activated carbon for COS removal should be 40°C. ‘The explanation for the result is considered to be as follows. In our previous work!®.71, it was found that the basicity and base strength of a catalyst predominantly affected the activities of COS hydrolysis, the basic centers seemed to be the exclusive reaction centers. ‘Thus, it could be deduced that KyCOs plays a role of active species. The removal of carbonyl sulfide by the activated carbon impregnated with KzCO3 was considered to be a hydrolysis process.156 Journal of Natural Gas Chemistry VoL8 No.2 1999 COS + HzO = CO; + HS HS, one of the products, was then adsorbed by the activated carbon. So it could be obtained from the above discussion that the modified activated carbon actually acts as cither a catalyst or an adsorbent. According to the Arrhenius equation, a small increase in temperature would result in a significant increase in the rate of the COS hydrolysis. Therefore, increasing the temperature of the sorbent bed would be beneficial to the COS removal. However, with the adsorption of HyS on the activated carbon, the active basic species would be lost slowly, which may cause the deactivation of. the impregnated activated carbon. When the sorbent temperature increased to a high level, for example, 60°C, the rate of hydrolysis was very fast, the amount of HS adsorbed on the activated carbon would reach a level, which probably lead to the thoughtful deactivation of the catalysts for COS hydrolysis reaction. This is in agreement with the experimental results shown in Fig.3. Due to the reasons mentioned above, there should be a favorable temperature for the removal of carbonyl sulfide by the K2CO3 modified activated carbon. Conclusions (1) Water vapor has a negative effect on the removal of carbon disulfide by organic amine modified activated carbon. (2) The experiment results show that 40°C is favorable for the removal of carbonyl sulfide by KpCO3 modified activated carbon. References Pierce, and R_N.Smith, Am. Chem.Soc., 73(1951)4551 RN.Smith, C.Pierce, and C.D Joer, J Phys. Chem., 58(1954)299 Pierce, and R.N.Smith, J.Phy.Collid Chem, 4(1950)784 N.Pechler, and G.Emig, Gas Separation & Purification, 5(1991)247 LSaleta, International Chemical Engineering, 16(1976)97 QLZhang, and H.X.Guo, Cuihua Xuebao (J.Catal.), 9(1988)14 QLZhang, and H.X.Guo, Cuihua Xuebao (J.Catal.), 9(1988)131 A AaweeNE180 Journal of Natural Gas Chemistry iPM Vol8 No2 1999 AS, SUE Ob BEATA SLICERS IE Il) BG LOOM: TERA CER A 650093: HARE ZH HM 650001) JLNatGas Chem, 8(1999)128 RAMUS A TARR TT — AMOI IZ. mPa HE. RZ EL LR, aa AR. RIAN LO TO UE RAR RAT TOR. ZR ERR ATRL AR AA Oe RAH IAO MER EA ROPER A. 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