Removal of Hydrogen Sulfide from Non-Condensable Geothermal Gas at Nesjavellir Power Plant

Kristn Vala Matthasdttir Department of Chemical Engineering, Lund Instituted of Technology, Lund, Sweden, June 2006
The non-condensable gas (NCG) from geothermal power plants can contain substantial amount of hydrogen sulfide, which has to be removed to meet environmental regulations in most location. However, in Iceland the NCG is emitted to the atmosphere without further treatment. In this paper, result of a masters study on different methods to remove H2S from NCG at Nesjavellir geothermal power plant is published. Four processes for H2S removal from NCG were studied, namely: WSA, LO-CAT, THOPAQ, and Fe-Cl hybrid processes. The first three processes are prevalent processes, but the Fe-Cl hybrid process is a recently developed process. The processes pre-design cost estimates are compared in order to choose an economic process for H2S removal from NCG at Nesjavellir power plant.
ABSTRACT: KEY WORDS:

H2S, Nesjavellir, Geothermal gas, Fe-Cl hybrid process,

1.

Introduction

The Icelandic nation has lived with the geothermal activity of the country through the centuries and the utilization of geothermal heat has been a part of the national culture for the last decades. Geothermal heat is one of Icelands greatest natural resources and utilization of geothermal energy is one of the most important aspects of daily life and public welfare in Iceland. Iceland is among the nations with the highest utilization of this energy resource, first only for residential heating and, more recently, also for the generation of electricity. Today, approximately 88% of Icelandic housing is geothermally heated and one fifth of the nations electricity is produced with geothermal steam. [1] Geothermal energy is a relatively environmental-friendly way for energy production. Harnessing of the geothermal heat produces minimal air emission, especially if compared to burning of fossil fuel. The emission is in form of dissolved gases such as CO2, H2S, N2, H2, CH4, O2 and Ar. The fraction of these gases in the steam depends on

the temperature in the area and the chemical composition of the ground, which can vary from one area to another. Carbon dioxide (CO2) is though always predominant followed by H2S. The amount of the other gases is relatively low. [2] Increased notice regarding environmental aspects reveals that the emission of H2S is quite large drawback for this energizer. The production of electric power from geothermal energy would be made environmentally friendlier if emission of the noxious gas H2S could be prevented. In this paper, result of a masters study on different methods to remove hydrogen sulfide from NCG at Nesjavellir geothermal power plant, is published. After a short introduction to the Nesjavellir power plant, a recently developed method, the Fe-Cl hybrid process is briefly described. Three prevalent H2S removal processes were chosen to compare to the Fe-Cl hybrid process. Finally, the processes predesign cost estimates are compared in order to choose an economic process for H2S removal from geothermal gas at Nesjavellir power plant.

2.

Nesjavellir power plant

3.

Fe-Cl hybrid method

Nesjavellir, in the Hengill area situated east of Reykjavk, is one of the largest hightemperature areas in Iceland. The geothermal activity is connected to three volcanic systems in this area. The Hengill system has erupted several times since the glacial age, the most recent 2000 years ago. Nesavellir is the biggest geothermal power plant in Iceland. The processing power of the power station is now 300 MWt, with the water production exceeding 1800 liters per second. In October 2005, the fourth electrical turbine was put into operation, making the total production of electricity 120 MWe. At Nesjavellir 22 holes have been drilled. Five of these have been permanently closed, while 17 holes are used for processing and measurements. The depth of the holes ranges from 1000 to 2000 metres, and temperatures of up to 380 C have been measured. The steam is taken to the power station at 12 bars and 190C and is conveyed to steam turbines where electricity is generated. The turbines are four, each produces 30 MWe of electricity. After the steam has been expanded, it is utilized to preheat cold water, to 85-90C in a condenser. The hot water is then transported in a pipeline to Reykjavk. The pipeline is over 23 km in length and has a diameter of 80 mm. The pipeline is designed for water up to 100C and can transport 1870 liters per second. It takes the water less than seven hours to flow from Nesjavellir to Reykjavk, with temperature decreasing less than two degrees. The NCG at Nesjavellir is vented into the atmosphere. Composition and amount of the main gases are displayed in table 1. [2] Table 1 Emission of geothermal gas at Nesjavellir power plant.[3]
Nesjavellir Composition (vol %) Amount [ton/year] CO2 45.4 15 400 H2S 26.5 6730 H2 28.1 440

An Icelandic group of scientists revived the Fe-Cl hybrid method, published in 1991 by a group of Japanese scientists, in order to remove H2S vented to the atmosphere at geothermal fields in an economical way. The process is still only on lab-scale. The process principle is to desulfurize H2S containing gas streams by absorption into a highly acid iron solution followed by electrolysis to regenerate the absorption solution and produce hydrogen. The process is capable of treating a gas stream involving a large amount of highly concentrated H2S that suits the environment at Nesjavellir. 3.1. Process chemistry Absorption H2S(g) + 2FeCl3 2HCl + 2FeCl2 + S Electrolysis 2FeCl2 + 2HCl H2(g) + 2FeCl3 3.2. Process description The process consists of three main stages: Chemical adsorption of H2S, separation of elemental sulfur and electrolysis (regeneration) of the liquid solution. The non-condensable gas is heated from 40C to 70C in a heat exchanger before entering a counter-current bubble column at atmospheric pressure. The H2S is chemically absorbed into the highly acidic FeCl2-FeCl3HCl solution. Simultaneously, ferric (Fe3+) ion is reduced to ferrous (Fe2+) and solid sulfur precipitates. Nearly a 100% turndown of H2S is reached at solution temperature 70-75C. [4] Measurements revealed that the H2 content of the NCG is not absorbed into the solution. The calculations are therefore only based on absorption of the H2S. For separation of the elemental sulfur, the scrubbing liquid enters a rotary drum vacuum filter where the sulfur is filtered out before the solution enters the electrolyzer. Sulfur causes corrosion on electrodes; consequently this is an important step. The temperature during the filtration should be kept at 70-75C.

Vent gas 10 9

8 Heat exchanger 3 Electrolyzer

H2

Absorption

Filtering 3 5 6

2 Heat exchanger 1 1 4 Sulfur

Heat exchanger 2

Figure 1 Flow scheme for Fe-Cl hybrid H2S Removal Process. 3.5. Process product The last stage, the electrolysis/regeneration of the absorption solution, is also the hydrogen production stage. After the filtration the solution is cooled to 50C in a heat exchanger. The solution is electrolyzed at voltages as low as 0.75-0.8 V for each cell in a bipolar electrolyzer. During the electrolysis H2 is evolved at the cathode, while ferric (Fe3+) is recovered at the anode by oxidation of ferrous (Fe2+). The solution is reheated to 70C in a heat exchanger before it is recycled back to the absorber. [4] 3.3. Material of construction The solution is highly acidic, which can create difficulties concerning selection of the material for construction. Here it is assumed that all equipment is made out of SS-316, which should be able to withstand the corrosive solution. [5] However, the solution may be too corrosive for the SS-316. Eventually the absorption column and piping can be made out of non-corroding material, such as polypropylene and polyethylene. Reciprocally, there is still uncertainty about material for the rotary drum filter and for heat exchangers. This has to be examined experimentally. 3.4. Catalysts / Chemical additives No proper catalysts are used in the process, although the iron ions can be taken as a catalyst. The iron serves as an electron donor / acceptor (a reagent) and as a catalyst that speeds up the reaction. The iron catalyst is not consumed in the process; only a modest amount of the iron solution is added to the process to replace mechanical losses and a small acid addition to ensure the alkaline state of the solution. The process has two products: sulfur and hydrogen gas. The sulfur can be used as landfill or in fertilizer manufacturing process. Hydrogen is a gas that is in high demand request nowadays. It can be used as fuel for special hydrogen cars and is therefore very valuable product. 4. Methods used for H2S removal from non-condensable geothermal gas Three prevalent H2S removal processes were chosen to compare to the Fe-Cl hybrid process, namely: WSA, LO-CAT, and THIOPAQ. These methods are shortly described below. 4.1. Wet gas Sulfuric Acid process - WSA A gas stream containing H2S can be converted into commercial quality sulfuric acid using the Haldor Topse - WSA process. First the sulfur-containing gas is incinerated to SO2 in a burner H2S + 3/2 O2 SO2 + H2O Next, the SO2 is converted to SO3 in a reactor containing one, two or more catalytic beds. The reaction is exothermal; therefore the gas is cooled between beds in order to optimize the SO2/SO3 equilibrium. SO2 + O2 SO3 After the last conversion stage, the gas is cooled, which allows SO3 to react with the water vapor to form gas phase sulfuric acid. [22] SO3(g) + H2O(g) H2SO4(l) The processs products are high quality sulfuric acid and steam. The produced amount of sulfuric acid is 20 000 ton/year (97.5 wt%). Produced steam, 60 000 ton/year (352C and

12 bars), can be combined to the power plants steam and used for electricity production. [6] 4.2. LO-CAT II Gas Technology Product LLC is the producer of the LO-CAT II process, a specific modification to the LO-CAT process, used to control H2S emissions from geothermal power plants with more than 99.9% H2S removal efficiency. The process is a wet scrubbing, liquid redox (reduction-oxidation) system that uses an iron solution to convert H2S to innocuous, elemental sulfur. The process operates with the stoichiometric ratio of iron (III) to hydrogen sulfide 2:1. The H2S is absorbed into a slightly alkaline solution. The H2S ionizes to bisulfide, which is further oxidized to elemental sulfur by reducing the iron ion from ferric (Fe3+) to the ferrous (Fe2+) state [7] HS- + 2Fe3+ S0solid + 2Fe2+ + H+ The ferrous ions are re-oxidized to ferric ions via contact with air, i.e. regeneration of the catalyst. [7] O2 + H2O + Fe2+ 2OH- + 2Fe3+ The processs product is ~ 4000 ton/year of 60 wt% sulfur cake. 4.3. THIOPAQ The Dutch company Paques B.V. has developed a process for desulfurization of H2S containing gas: The process is a biotechnological process for removing H2S from gaseous streams and has over 99.5% sulfur removal efficiency. The H2S containing gas enters a wet scrubbing, packed absorption column. The gas is desulfurized in a counter-current flow with a slightly alkaline (pH 8-9) solution. H2S(g) + OH HS (l) + H2O The adsorbed sulfide is oxidized to elemental sulfur by naturally occurring microorganisms of gene Thiobacillus. [8] HS- + O2 S0 + OHThe sulfur particles are separated and dewatered in a sulfur recovery unit. The product is ~ 6000 ton/year biosulfur with 6065% solid content. 5. Cost Estimation
-

are pre-design cost estimates of a limited addition to the existing power plant at Nesjavellir. Meaning that the estimate includes all process equipment but excludes provision of storage, land, utilities, administrative buildings and auxiliary facilities. The accuracy of the estimate is 30%, but should nevertheless sufficiently accurate to provide a reliable decision. [5] A process bid from manufacturers were obtained for the WSA, LO-CAT II, and THIOPAQ processes. As the Fe-Cl hybrid process is still on lab scale the process equipment cost were calculated from special diagrams, material- and pressure-factors. Sizes and specifications of all equipment were calculated along with material- and energy balances. F.C.I. include all process equipment and all cost concerning installation of equipment, piping and electricity. This cost will be financed with bank loan. Table 2 - Facts about the loan Pay beck period 10 years Months per year 12 (equal) Nominal interest rate 5% Revenue come from the sale of the product produced by the plant. Table 3 - Product prices
Product Electricity Sulfuric acid Sulfur Hydrogen 3 ISK/kWh 80 $/ton[9] 26 $/ton[9] 0.49 $/m3

Total production cost is defined as the total costs of operating the plant, recovering the capital investment, and maintenance and repair cost. Table 4 - Cost data for utilities
Utilities Electricity Cooling water1 Hot water (~100C)2 1.5 ISK/kWh 0 ISK/m3 0 ISK/m3

In order to choose a suitable process for the elimination of H2S in Nesjavellir, the cost of each process was determined. The estimates

1 2

Excess cold water from the power plant can be used.

A considerable amount of 100C hot water is released

from the power plant every second, part of that can be used for appropriate process

6.

Conclusion and Discussion

transportation would be too expensive for this project. Although the Fe-Cl hybrid process turns out to be the optimum process, it still has many unsolved factors since the process is still on a lab scale. The material of construction is one factor, e.g. the solution is highly acidic which can cause problems concerning the selection of material. This can affect the fixed-capital investment cost greatly. Furthermore, the electrolysis cell is not fully developed. The acidic condition and the amount of electrolyte will definitely affect the design of the cell. Experiments concerning absorption of H2 into the solution need to be continued. If the experiments reveal that H2 absorbs partly or fully into the solution, it greatly affects the size of the absorption column, the amount of absorption solution, and the size of the anode area of the electrolysis cell. Finally, the processs feasibility is based upon the price for hydrogen, i.e. variations in hydrogen prices highly affect the financial return on the process. The cost estimate demonstrates however, that the Fe-Cl hybrid process should be taken to the next design level, which should be the construction of a pilot plant.

With ever increasing industrialization in Iceland the demand for electrical energy grows. One way to meet this need is to harness geothermal energy. This is an environmentally friendly way to produce energy. Quite a serious drawback for this energy type is the emission of H2S. The production of electric power from geothermal energy would be made environmentally friendlier if emission of the noxious gas H2S could be prevented. The cost estimate gives a clear conclusion. The Fe-Cl hybrid process has the lowest startup cost, fixed capital investment, and is the only process that generates profit. The biggest advantage of the Fe-Cl hybrid process in this comparison is the production of hydrogen. Hydrogen is in high demand nowadays as an environmentally friendly automobile fuel. Table 5 compares the conclusions from the cost estimates each of the four processes. Of the other processes, the Haldor Topses WSA process could be a feasible option, but only if a domestic purchaser can be found. Transport of sulfuric acid between countries and all that is entailed following the Table 5 - Comparison of the processs cost estimates.
[Millions ISK/year] F.C.I. Revenue Cost Loan payment Production cost Annual Cost Profit / Loss WSA 1250 140

LO-CAT 1600 7.5

THIOPAQ 640 12

Fe-Cl hybrid 500 160

162 43 205 -65

205 105 247 -302.5

82 55 137 -125

63 35 98 62

Nomenclature NCG (g) (l) SS-316 Non-condensable gas Gas phase Liquid phase Stainless steel 316

References [1] Baradttir, H. (2004). Energy in Iceland Historical Perspective, Present Status, Future outlook. Orkustofnun. [2] rmannsson, H. (2001) Gastblstur fr jarhitasvum, Lecture at Orkuing 2001. (pp. 324-330). [3] slenskar Orkurannsknir. 2005). Website: www.isor.is. (July

[4] Mizuta, S., Kondo, W., Fujii, K., Iida, H., Isshiki, S., Noguchi, H., et. al. (1991). Hydrogen Production from Hydrogen Sulfide by the Fe-Cl Hybrid Process. Industrial & Engineering Chemistry Research, 30, 16011608. [5] Peters, M.S., Thimmerhaus, K.D., West, R.E. (2003). Plant Design and Economics for Chemical Engineers. (5th ed.). (Chapter 6, pp. 521-536, pp. 859-864,). Boston, USA. McGraw-Hill Higher Education. [6] Laursen, J.K. Sulfur removal by the WSA process, [WWW document]. URL http://www.topsoe.com/site.nsf/vALLWEBDO CID/KVOO-5PGFB7/$file/EnvWSAdownl422pdf.pdf [7] Heguy, D.L. & Nagl, G.J. (2003) Consider optimised iron-redox processes to remove sulfur: New processing developments are overcoming operational obstacles of older units. Hydrocarbon Processing, January Issue, pp. 53-57. [8] Zessen E., Benschop, A., Jannesse, A., Keizer, A., Heine, B., Peace, J., Abry, R. (2004). Application of THIOPAQTM biosulphur in agriculture. Paques B.V. [9] The Innovation Group. Website: http://www.the-innovationgroup.com/welcome.htm. March 2006