Optimisation of WSA technology

- Integration of energy and adaptation to the Chinese market Annette Wendt

Department of Chemical Engineering, Lund University
Abstract The aim of this Master thesis was to optimise the WSA technology in two areas; integration of energy and to adapt the design for the Chinese legislation demands. The process contains combustion, catalytic oxidation, hydration and condensation, which are all exothermic reactions. The pinch technology was used to investigate if there could be improvements in the heat recovery. The result illustrated that there could be improvements in the heat recovery if the outlet stack gas temperature was lowered and the excess heat was used for more steam production. In order to decrease the heat exchanger area and thereby lower the investment cost, the steam superheater could be placed before the waste heat boiler. China is a growing market for the WSA process. The operating conditions should therefore be adapted to meet the Chinese legislation demands in a more economic way. In order to find the optimal design the combustor temperature, the concentration of H2S in the inlet acid gas and the capacity of the WSA plant were studied. The result was that the investment cost decrease with a decreased combustor temperature, a decreased concentration of H2S and a decreased capacity. If the investment cost was studied per ton produced sulphuric acid, it decreased with a decreased combustor temperature, an increased concentration of H2S and an increased capacity. Introduction This master thesis has been carried out at the Department of Chemical Engineering in cooperation with the company Haldor Topse A/S. The environmental WSA (Wet gas Sulphuric Acid) plant has been optimised in two areas. The process is used for cleaning off-gasses from various industries with a content of sulphur. The heat released by the exothermic reactions is utilised for steam production and process-toprocess heat recovery. In the first part of the optimisation the main focus was to investigate if there could be improvements in the heat recovery using the Pinch technology. In the second part an economical optimum should be determined for design of the process to meet the demands in the Chinese legislation. China is a large market in the desulphurization area and it continues to grow. A more economic process adapted to their legislation demands would be more competitive and could thereby lead to an increased market share. The WSA process A box diagram over the various steps in the WSA plant is illustrated in figure 1 [1].

Figure 1: A box diagram over the various steps in the WSA process.

The inlet sulphurous off-gases are led to a combustor were they are mixed with combustion air. In the combustor the hydrogen sulphide is converted to sulphur dioxide according to the following exothermic reaction: H2S + 3/2 O2 H2O + SO2 + 515 kJ/mole (1) The hot process gas leaving the combustor is cooled in a waste heat boiler and then it is cooled once again in a steam superheater. The cooled SO2 containing gas is led to the SO2 converter where it is converted to SO3 in three adiabatic catalytic beds [2]. In the converter the SO2 is oxidized to SO3 according to: SO2 + 1/2 O2 SO3 + 99 kJ/mole (2)

The reaction is a temperature and pressure dependent equilibrium reaction. In order to achieve a high conversion the reaction is cooled in two interbeds. After the third catalyst bed the process gas is cooled by boiler water. During this cooling part of the formed SO3 reacts with the water vapour present in the process gas according to the following exothermic hydration reaction [2] : SO3 (g) + H2O (g) H2SO4 (g) + 101 kJ/mole (3) After the SO2 converter the process gas is led to the WSA condenser were it is cooled by ambient air. During the cooling the remaining hydration reaction and condensation of the sulphuric acid takes place: H2SO4 (g) H2SO4 (l) + 50.5 kJ/mole (4)

the target temperature. [4] The differential heat flow added or reduced to a stream during heat exchange, will increase or reduce the heat content on the stream. The change in heat content from a supply temperature to a target temperature is calculated by equation 1.

& & Q = m C p dT =m C p (TT TS )

TS

TT

(1)

The slope of the line in the T/H diagram represents the stream and is calculated by equation 2.

dT 1 1 = = & C p CP dQ m

(2)

The condensed hot sulphuric acid is further cooled in a heat exchanger cooled by cooling water. The acid is of commercial quality. The clean process gas leaves the condenser at the top. The heat released by all the exothermic reactions in the WSA plant is recovered in the form of steam. [2] The concept of pinch analysis The Pinch technology is a strategic method based on fundamental thermodynamic for optimising the heat exchange between hot and cold streams in a process plant. In that way the need for external heating and cooling is minimised. [3] A helpful way of visualise the cooling and heating demand of a stream is the temperature/heat content-diagram, most often called composite curve, see figure 2.

When the heat content in each temperature interval is summarized, multiple streams are hand able. This is calculated by equation 3.

& ((m C

p line1

& + (m C p ) line2 ) (T2 T1 )

(3)

This method for generating composite curves and achieves the minimal energy targets were applied on the WSA process. Method A pinch analysis was applied on the process. The data used in the analysis was extracted from a flowsheet and was assumed to be fixed data.
1.

2.

3.

The first pinch analysis was carried out the studied flowsheet. The studied flowsheet contained a lot of heat in the clean outlet process gas. The produced acid was cooled by recirculation of cold acid and then heat exchanged to the target temperature. The second attempt had a decreased temperature of the outlet clean process gas and only heat exchange of the produced acid of was investigated. A third attempt had also a decreased temperature of the outlet clean process gas but the same acid cooling procedure as in the studied flowsheet was carried out in order to compare the solutions.

Figure 2. A composite curve visualising the minimal energy demands and the pinch temperature.

Area calculations for the heat exchangers in the three attempts were the carried out. Results Pinch analyse The composite curve for the first pinch analysis is seen in figure 3. There it is received that there is no overhang at the right side of the curve and thereby no need for hot utility. On the left side

Since the change in heat content, Q, during the heat exchange is the only thing that is interesting, a given stream can be plotted anywhere on the heat content axis providing it has the correct slope and goes from the supply temperature to

there was an overhang and that overhang represents the demand for cold external utility.

Minimum cold utility: 2939 kW The difference between direct cooling in a heat exchanger and cooling by adding cold acid and then heat exchange was small. There were less heat that could be used for an increased steam production in the third attempt but the decrease was not very noteworthy. When the areas was calculated for all the heat exchangers the result was that the area decreased with 50 % if the heat exchanger for superheating the steam was placed before the waste heat boiler instead of after it.

Figure 3. Composite curve for the first pinch analysis.

That gave the following result in the first pinch analysis: Pinch temperature: 1170C Minimum hot utility: 0.0 kW Minimum cold utility: 727 kW In the second attempt the decreased temperature of the clean outlet process gas increased the overhang at the left side, see figure 4.

Chinese legislation The Chinese legislation that covers the studied process plant is GB16297-1996. The WSA plant is counted in category of plant that produces sulphuric acid and plants that has applications of nitrogen oxides. That results in the following legislation demands: < 960 mg SO2 / Nm3 < 240 mg NOx / Nm3 Method The parameters varied to find an economic optimum for the Chinese market was: The combustor temperature, 1000C; 1200C; 1400C Concentration of H2S, 20%; 25%; 30% Capacity of the plant, 1200 Nm3/h; 2400 Nm3/h; 4800 Nm3/h In each simulation the amount of SO2 emitted was optimised to the legislation demand. The varied operating conditions demanded a changed design of the process equipment. The equipment that was cost estimated after each simulation was: heat exchangers SO2 converter WSA condenser The amount of catalyst was also included in the cost estimation. Results adaptation to Chinese market The investment cost as a function of the capacity of the WSA plant is received in figure 5. The investment cost per ton produced sulphuric acid decreases with a decreasing capacity along with a high combustor temperature and high concentration of H2S.

Figure 4. Composite curve for the second pinch analysis.

The energy targets became the following: Pinch temperature: 1170C Minimum hot utility: 0.0 kW Minimum cold utility: 3073 kW The increased energy demand indicated that there could be an increase in steam production. This hot stream could be used for preheating the inlet boiler water that was used for cooling the gas several times in the process and thereby generate superheated steam. In the third pinch analysis the difference by carrying out the cooling with recirculation gave the following results: Pinch temperature: 1170C Minimum hot utility: 0.0 kW

30%, 1000 C 25% 1000 C

Cost in percentage of base case/ ton produced H2SO4

20% 1000 C 24 30%, 1200 C 25%, 1200 C 20%, 1200 C 22 30%, 1400 C 25%, 1400 C 20%, 1400 C 20

temperature. In this case as well the large capacities and concentrations resulted in the lowest cost. For high capacities the trend is broken between 1200C and 1400C were the cost deceases for high combustor temperatures in a couple of cases. The total investment cost was the opposite for the capacity and concentration of H2S, the lower concentration and capacity the lower investment cost. A low combustor temperature did however still lead to the lowest investment cost. Conclusions The conclusion of the pinch analysis is that there are winnings possible to do in the WSA process. There is excess heat when the temperature of the clean outlet process gas is decreased. That heat could be used for an increased steam production, which would improve the heat recovery. The investment cost for the heat exchanger network, could be lowered if the steam superheater was placed before the waste heat boiler. The conclusion from the optimisation of the operating conditions to achieve an economical process design was: 1. For the investment cost per ton produced sulphuric acid: optimal operating conditions are identified at low combustor temperatures, high concentrations of H2S and high capacities of the WSA plant. For the total investment cost: optimal operating conditions are identified at low combustor temperatures, low concentrations of H2S and low capacities of the WSA plant.

18

16

BASE CASE
14

1200

2400

4800

Capacity (Nm3/h)

Figure 5. Investment cost per ton produced sulphuric acid as a function of the capacity of the plant.

The investment cost per ton produced sulphuric acid as a function of the concentration of H2S in the inlet gas is received in figure 6. From the figure it is received that the higher concentration the lower investment cost per ton produced sulphuric acid. The trend is weaker when the concentration increases.
1000C 1200Nm3/h 1200C 1200Nm3/h

Cost in percentage of base case /ton produced H2SO4

24

1400C 1200Nm3/h 1000C 2400Nm3/h 1200C 2400Nm3/h 1400C 2400Nm3/h 1000C 4800Nm3/h 1200C 4800Nm3/h 1400C 4800Nm3/h

22

20

18

16 BASE CASE 14

20

25 Concentration (% H2S)

30

2.

Figure 6. Investment cost per ton produced sulphuric acid as a function of the concentration of H2S

The investment cost per ton produced sulphuric acid as a function of the combustor temperature is showed in figure 7.
Cost in percentage of base case /ton produced H2SO4 26 30% 25% 20% 30% 25% 20% 30% 25% 20% 1200Nm3/h 1200Nm3/h 1200Nm3/h 2400Nm3/h 2400Nm3/h 2400Nm3/h 4800Nm3/h 4800Nm3/h 4800Nm3/h

24

22

20

18

Prospective Investigate the pinch if electricity was produced from the superheated steam. Vary less operating conditions in the economic optimisation. That would make it easier to understand the economic trends for the single equipments. Study the SO3 content in the outlet of the converter. Acknowledgements This work has been carried out at Haldor Topses environmental department with Jane Albertus Steenberg and Morten Mejlholm as supervisors, they are gratefully acknowledged along with Prof. Stig Stenstrm, Dep. of Chem. Eng., Lund University who was examiner.

16 BASE CASE 14

1000

1200 Combustor temperature (C)

1400

Figure 7. Investment cost per ton produced sulphuric acid as a function of the combustor temperature.

The investment cost per ton produced acid increases with an increased combustor

Table of Symbols c P = Specific heat capacity (kJ / kg / C ) CP = heat capacity flowrate (kW / C ) & m = mass flow (kg / h ) T = temperature (C ) Q = heat flow (kW ) References
Haldor Topse A/S, (2007); VK Series Sulphuric acid Catalysts for Today and for the Future; brochure
2

Andersson, P., (1998), Optimisation of heat exchanger networks, Course material for KET010, Institution of Chemical Engineering, Lund, Kemp, I.C., (2007), Pinch Analysis and Process Integration, Elsevier Ltd, second edition, chapter 1-4, 6-8
5 3

Wendt, A., (2008), Optimisation of WSA technology, Department of Chemical Engineering, Lund University

MOHN, (2007); Process Description; Job S-01403; Haldor Topse