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Regeneration and Activity Test of Spent Zinc Oxide Hydrogen Sulfide Removal Catalyst
Karim.H.Hassan Department of Chemistry, College of Science, University of Diyala, Baquba, Iraq Abstract Two methods were experimented to regenerate the spent ZnO catalyst. The first one involved combustion by air while the second one involved steam treating of catalyst. The results abstracted from the first method showed that it is not suitable and reliable in regeneration of the catalyst because of the formation of zinc sulphate which cause blockage of the catalyst pores and hence reduce its activity. The steam regeneration method seem to be very practical and promising as the catalyst regenerated have a good activity which approached 97 %, in addition, the physical and chemical properties of the regenerated catalysts was very close and similar to the commercial new one Keywords: Regeneration, Spent zinc oxide, Hydrogen sulphide, Catalyst, Activity
1. Introduction
The natural gas composed of light hydrocarbons in which methane is the major one. As far as the sulfur compounds are concerned hydrogen sulfide is the important one with carbonyl sulfide, carbon disulfide and mercaptans. The chemical composition of an Iraqi natural gas reported in Basraha refinery, 1990 is given in table (1).
Table 1: Chemical composition of Khor Al-Zubair natural gas, H2S in ppm
Gas Vo1%
N2 0.95
CO2 2.63
C1 73.82
C2 10.95
C3 8.44
iC4 0.68
nC4 1.34
iC5 0.25
nC5 0.41
C6+ 0.53
H2S 0.62
Hydrogen sulfide has unpleasant odor and corrosive, Cadena,F and R.W.peters (1988) in addition of being poison for most industrial catalysts, so it has to be removed from industrial gases and the methods used to do so can be classified as old method by Iijima, Masaki , Kobayashi, Kazuto, Morita, Kazuhiro, 2004 and new methods by Susan, 1989, the first one includes the phosphate method, iron oxide method and sodium hydroxide method and the second one used activated carbon adsorption, molecular sieve and zinc oxide. The activated carbon was used to adsorb or separate hydrogen sulfide and other gases from natural gas in a fixed bed reactor where two or three reactor were connected some of them for adsorption of gases and the other for regeneration of the deactivated bed. Owing to increase of the heavy hydrocarbon gases in the natural gas in recent years which cause to decrease the life time of the activated carbon as adsorbent and required high temperature for regeneration, the use of activated carbon process became limited. Molecular sieve method is very limited and not widely used. C
Regeneration and Activity Test of Spent Zinc Oxide Hydrogen Sulfide Removal Catalyst
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Zinc oxide method is the most important one. It is used to remove the traces amount hydrogen sulfide being present in the gas mixture that enter the primary and secondary steam reforming units and the secondary CO to CO2 converter i.e. it acts as a guard to prevent all the catalysts used in fertilizer industry from poisoning with sulfur present in the feed. The natural gas or naphtha feed were heated to 285-400 C and then passed through one or more bed of ZnO in the form of tabletes, spheres, or extrudates where the function of the catalyst depends on the chemical reaction: ZnO + H2S ZnS + H2O (1) Usually zinc oxide catalyst is used as a mixture of ZnO and alumina as a binder in addition to some filler. In general 90 % wt of ZnO is quiet acceptable. On using naphtha as feed the sulfur being reduced to 0.02 ppm whereas with natural gas as a feed the sulfur can be removed to a level of 0.1 ppm. At ordinary condition and with out side interferences the adsorption capacity can be theoretically approach 41.7 Kg H2S/100Kg catalyst or 39.5 Kg of S if it contain 100 % ZnO. The catalyst loose its activity suddenly when the H2S concentration is high enough as a result of the formation of ZnS layer on the external surface and then filling the pores and preventing the next coming H2S to pass and react with new ZnO. Most sulfur removal reactors consist of two beds of catalysts the first one is CoMo catalyst that convert the sulfur compounds by hydrogen to H2S, 'Man Haimour, Ribhi El-Bishtawi and Abdulrakib Ail-Wahbi (2005) and Elvers, Barbara et al. (1989) and the second one is ZnO bed where H2S is being adsorbed on. Catalysts deactivation are governed by several factors and the three most important are poisoning, fouling and sintering of the catalysts. Using a huge amount of catalysts with very high costs in industry necessitates studying and developing methods for regeneration. Most catalysts regeneration processes fall into two categorizes which are the oxidative regeneration and non oxidative regeneration as classified by Furimsky.E and F.E.Massoth, (1993).The oxidative one involves treatment or exposing the waste catalyst to oxygen diluted by N2 and / or steam, CO2, N2O, O3. The non oxidative one involves treatment of the waste catalyst with selective solvents that are capable of removing the contaminants from the surface of the catalysts with out effecting the distribution and the percent of the active centers and the active materials of the catalysts. Regenerability of ZnO discussed by Susan (1989) is restricted by loss of surface area at high regeneration temperatures and formation of zinc sulfate at low regeneration temperatures. Also, during sulfidation , reduction of ZnO followed by vaporization of elemental zinc can take place at temperatures below 600 C. Of important works on the regeneration of the ZnO catalysts was done by Susan and Copeland.R,J, M. Cesario, D. Feinberg, B. Windecker and J. Yang] by preparing a regenerable Zinc oxide -Titanium dioxide sorbents for high temperature H2S removal from fuel gases. Sulfidationregeneration cycles of ZnO- and CaO containing sorbents were conducted to examine the hydrogen sulfide removal performance by Sophia E.A. Evangelos , and Vasalos.A, Iacovos (1995). Regeneration of sulfided metal oxide absorbent in an absorber is conducted using as diluents for oxygen a portion of Claus plant gas-in-process withdrawn upstream of the absorber. The result is a reduction in the size of the absorber and/or a reduction in the rate of return of regeneration effluent to a Claus plant during regeneration of such absorbent, Mcgalliar.L.Russell (1988). ZnO was Prepared from zinc nitrate by precipitation and the performance and kinetic studies were done by Karim. H.Hassan , Z. A-A Khammas and A. M. Rahman (2008) where activation energy and enthalpy of activation were calculated. The aim of the present investigation is to establish a new, practical method to regenerate the spent ZnO catalyst and test its activity.
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Karim.H.Hassan
Regeneration and Activity Test of Spent Zinc Oxide Hydrogen Sulfide Removal Catalyst
Figure 1: Flow diagram of laboratory hydrodesulphurization and regeneration units
1-feed tank for naphtha 2-Ball valve 3-Pump 4-One way valve 5-Heater 6-Pressure gauge 7-Pressure control valve 8-Heaters 9-Temp. thermocouples 10- Reactor 8 0utlet gas 1 To heating control 2 3 4 7 heater To temperature control Thermocouple 9 9
292
10
tubular furnace
reactor
5 H2
2.3.2. Steam Regeneration Method The spent catalyst is placed as a bed in the tubular reactor. The steam generated from water and a nitrogen gas was mixed with a ratio of 2:1 and passed inside the reactor at flow rate of 5 liter/hour, the produced gases from reaction were sent to a set of traps that contain cadmium sulfate solution to trap the hydrogen sulfide formed. The experiment run until the generation of hydrogen sulfide ceased. 2.4. Catalyst characterization The metal content of the catalysts were determined by standard atomic absorption methods. The Bulk density was determined by placing a weight catalyst in a graduated cylinder then shakes it by vibrator and read the volume of it and then calculate the density i.e. it is the packing or load density of the reactor. The particle density is measure by weighting a symmetrical extrudate and calculate its volume. It is carried out for several particles and takes the average. Pore volumes and skeletal density was determined by the liquid impregnation methods described by Richardson (1982) while porosity is calculated theoretically from densities values. Hardness was determined with the ERWEKA.TBH28 hardness meter while crushing value was determined by placing 25 gm of the sample under pressure of 18 kN for 20 minutes and measure the amount of powder that pass through 53 micrometer mesh as a percent relative to the total weight. 2.5. Catalyst Testing Activities of the catalysts for the adsorption of H2S were determined using a plant that consists of two units the first one for generation of the hydrogen sulfide by the hydrodesulphurization (HDS) of naphtha that contain 0.07 % wt of sulfur using a CoMo catalyst and the second one for the adsorption of the H2S on ZnO catalyst. The schematic representation of the plant is well described by Karim et.al. and shown in fig.1.Test conditions were reaction temperature 340 C , pressure, 25 bar and flow rate of naphtha was adjusted so that the gas leaving HDS unit contains 0.00277 gm H2S /liter by maintaining the flow rate of the gas leaving the HDS unit at 10.8 liter / hour or 0.028 gm H2S /hour.
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Karim.H.Hassan
Regeneration and Activity Test of Spent Zinc Oxide Hydrogen Sulfide Removal Catalyst
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So we can conclude that it is possible to use steam heated at 800 C to regenerate the spent ZnO catalyst and renew and refresh its characteristics and use it again with a good activity.
Table 2:
Properties Form Color Size (mm) Bulk density,gm/cm3 Porosity Pore volume cm3/gm Hardness, N Crushing value % wt ZnO % ZnS % ZnSO4 % Al2O3% gm H2S/gm catalyst
500 C same grey 4x5 1.211 0.11 0.11 9.5 8.0 20.7 67.5 1.8 10 0.09
800 C same yellow 4x5 1.230 0.12 0.14 12 6.5 40.5 26.1 23.4 10 0.05
Table 3:
Properties
Form Color Size (mm) Bulk density, gm/cm3 Particle density, gm/cm3 Skeletal density, gm/cm3 Porosity Pore volume, cm3/gm Hardness, N Crushing value, % ZnO, % ZnS % ZnSO4 % Al2O3, % Zn, % Al, % gm H2S/gm catalyst Activity , %
Spent Extrudates Grey 4x5 1.45 2.40 3.33 0.15 0.10 9 8.0 0.0 91.51 0.0 8.49 72.22 5.29 0.0 0.0
Commercial Extrudates White 4-5 x 5-7 1.18 2.20 3.25 0.28 0.23 10 8.5 90 0.0 0.0 10 72.22 5.29 37.73 100
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Karim.H.Hassan Basraha refinery, 1990, Internal report, Southern Refineries Company, Iraq Cadena,F and R.W.Peters,1988, Evaluation of chemical oxidizer for hydrogen sulfide control, J Water Poll Control Fed 60, 7 , pp1259-1263 Copeland.R.J, M. Cesario, D. Feinberg, B. Windecker and J. Yang, TDA Research Inc, Wheat Ridge, Colorado 80033. Elvers, Barbara et al, 1989, Ullmann s Encyclopedia of Industrial Chemistry, Volume A12, page 192. Furimsky.E and F.E.Massoth, 1993, Catalysis Today, 17, 4, pp 537-659. IP standards for Petroleum and Its Products", 1976, The institute of Petroleum, England , 3rd Edition. Karim. H.Hassan , Z. A-A Khammas and A. M. Rahman, 2008, Al-Khwarizmi Engineering Journal, Vol.4, No.3, pp74-84. Iijima.M , Kobayashi. K and Morita, K, 04/27/2004, United States Patent 6726852 , Application Number: 09/801720. 'Man Haimour, Ribhi El-Bishtawi and Abdulrakib Ail-Wahbi, 2005, Desalination, 181, pp145152. Mcgalliar.L.Russell ,1988, United States Patent 4769229, (Broken Arrow, OK) , Application Number: 06/912023. Richardson.J.T , 1982, "Principles of Catalyst Developments", University of Houston. Sophia.C , Evangelos.E.A ,and Vasalos.A, Iacovos ,1995, Publisher: American Chemical Society, Publication Name: Environmental Science & Technology, Subject: Science and technology, ISSN: 0013-936X, Susan, L, J.Kandaswami. and F.S.Maria, 1989, Ind.Eng.Chem.Res, 28, 535 Vogel,A.I,1978, "Vogel's Textbook of Quantitative Inorganic Analysis", 4th Edition, Longman Scientific & Technical, London.
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