Method for inter-bed cooling in wet gas sulfuric acid plants
11543120 · 2023-01-03
Assignee
Inventors
Cpc classification
B01J2208/00168
PERFORMING OPERATIONS; TRANSPORTING
Y02P20/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01D2257/306
PERFORMING OPERATIONS; TRANSPORTING
C01B17/775
CHEMISTRY; METALLURGY
F22B1/18
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J8/0496
PERFORMING OPERATIONS; TRANSPORTING
International classification
F22B1/18
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
B01J8/04
PERFORMING OPERATIONS; TRANSPORTING
Abstract
In a method for cooling of process gas between catalytic layers or beds in a sulfuric acid plant, in which sulfuric acid is produced from feed gases containing sulfurous components like SO.sub.2, H.sub.2S, CS.sub.2 and COS or liquid feeds like molten sulfur or spent sulfuric acid, one or more boilers, especially water tube boilers, are used instead of conventional steam superheaters to cool the process gas between the catalytic beds in the SO.sub.2 converter of the plant. Thereby a less complicated and more cost efficient heat exchanger layout is obtained.
Claims
1. A method for cooling of process gas between catalytic beds in a wet gas sulfuric acid plant, in which sulfuric acid is produced by condensation of H.sub.2SO.sub.4 from a feed stream, wherein the feed stream comprises at least one of a feed gas containing sulfurous components and a liquid feed containing sulfurous components, wherein at least one boiler is used to cool the process gas between the catalytic beds in a SO.sub.2 converter of the plant.
2. The method according to claim 1, wherein the at least one boiler is a water tube boiler.
3. The method according to claim 2, wherein the orientation of the water tube boiler is approximately horizontal.
4. The method according to claim 3, wherein the water tube boiler comprises tubes in a tube bank, wherein the tubes are bare, fitted with fins or have a combination of finned and bare tubes in the tube bank.
5. The method according to claim 2, wherein the water tube boiler is provided with a process gas side bypass in order to be able to control the inlet temperature to a downstream catalyst bed.
6. The method according to claim 5, wherein the bypass is internal.
7. The method according to claim 5, wherein the bypass is external.
8. The method according to claim 2, wherein the water tube boiler is placed within a shell of the SO.sub.2 converter.
9. The method according to claim 1, wherein the process gas originates from combustion of at least one feed stream of spent sulfuric acid.
10. The method according to claim 1, wherein the feed stream is a CS.sub.2 and H.sub.2S containing gas from a viscose fiber production plant.
11. The method according to claim 1, wherein the inlet temperature to a downstream catalyst bed is controlled by using a mixer to equalize a temperature difference.
Description
(1) In the following, the invention is described in more detail with reference to the attached Figures, where
(2)
(3)
(4)
(5)
DESCRIPTION OF A WSA PLANT FOR THE TREATMENT OF VISCOSE OFF-GASES
(6) A typical wet gas sulfuric acid (WSA) plant, configured for the treatment of a CS.sub.2 and H.sub.2S containing lean gas from a viscose fiber production plant and producing sulfuric acid, is shown in
(7) The lean gas (1) is split into two parts, of which about ⅓ is sent to the thermal combustor (6) via line (3), where it is combusted together with fuel gas (7) which is needed to maintain a sufficiently high temperature in the combustor. The required oxygen for the combustion is contained in the lean gas. In addition to that, molten sulfur (8) can be fed to the combustor to boost the acid production and heat input to the combustor. The remaining ⅔ of the lean gas (4) bypasses the combustor and is used to quench the combustor flue gas (11) which is then fed to the SO.sub.2 converter (12). The CS.sub.2 and H.sub.2S contained in the by-passed lean gas is oxidized to SO.sub.2, CO.sub.2 and H.sub.2O in a first adiabatic catalytic bed (13) active for complete oxidation of H.sub.2S and CS.sub.2. The heat of oxidation of H.sub.2S and CS.sub.2 will typically increase the process gas temperature by 80-150° C.
(8) The SO.sub.2-containing process gas now enters the first adiabatic SO.sub.2 oxidation bed (14) which is loaded with sulfuric acid catalyst active for oxidation of SO.sub.2 to SO.sub.3. In the first SO.sub.2 converter bed, the majority of the SO.sub.2 is oxidized to SO.sub.3, which increases the process gas temperature at which the highest possible SO.sub.2 conversion is below the emission requirements and thus a cooling step and another conversion step is required. In the inter-bed cooler (15), the partially converted process gas is cooled to the optimum inlet temperature of the second SO.sub.2 converter bed, where the final SO.sub.2 conversion takes place, bringing the overall SO.sub.2 conversion into the 98-99.5% range. The process gas is then cooled in the process gas cooler (17) before it is sent to the WSA condenser (19). In the process gas cooler, SO.sub.3 is partially reacting with H.sub.2O to form gaseous H.sub.2SO.sub.4. In the WSA condenser, the process gas is cooled to about 100° C., the hydration of SO.sub.3 to H.sub.2SO.sub.4 is completed, and H.sub.2SO.sub.4 is condensed to form liquid concentrated H.sub.2SO.sub.4 which leaves the WSA condenser via line (40). The clean gas leaves the WSA condenser via line (20). The clean gas may be sent for additional SO.sub.2 removal in e.g. a caustic or peroxide scrubber or an acid mist filter (not shown in
(9) The cooling medium for the WSA condenser is ambient air (31) compressed in the cooling air blower (33) and sent to the WSA condenser via line (34), leaving the WSA condenser via line (35).
(10) For such a plant, heat recovery is of great importance. To save fuel gas and reduce the size of the combustor, only a fraction of the lean gas is combusted thermally, the major part of the lean gas being combusted catalytically in the first catalyst bed (13). The alternative would be all lean gas going to the combustor, significantly increasing the fuel gas consumption and the size of the combustor, which would require a waste heat boiler to cool the process gas to the SO.sub.2 converter inlet temperature. The heat released in the combustor and the catalytic converter beds is modest and not sufficient to produce sufficient amounts of high pressure saturated steam required in the inter-bed cooler, and thus a quite complex thermal management system will be needed to maximize the production of saturated steam to the inter-bed boiler.
(11) Demineralized water (50) is sent to the de-aerator (51) where oxygen is stripped off using low pressure steam (52) The deaerated boiler feed water leaves the deaerator via line (56) and the pressure is increased by the boiler feed water pump (57). The boiler feed water (58) is then preheated in the boiler feed water preheater (59) before it goes to the steam drum (62) via line (61). A small part of the boiler feed water is used for quenching the export steam (75). The high pressure steam drum is connected to two boilers, namely the process gas cooler (17) and the steam generator (80). Saturated steam leaves the steam drum via line (72), and it is superheated in the inter-bed cooler (15). The superheated steam is then sent to the steam generator (80) via line (73), where it is de-superheated, while saturated steam is produced in the steam generator. A part of the de-superheated steam is sent to the boiler feed water (BFW) preheater (59) where the steam is condensed and the heat is used for preheating the boiler feed water. The steam condensate leaves the BFW preheater via line (77) and is returned to the deaerator (51). The remaining partially de-superheated steam (75) is throttled to the desired export steam pressure and quenched to near saturation using boiler feed water from line (63) and sent to battery limit as export steam via line (64).
(12) The described highly efficient and integrated heat management system is necessary to provide sufficient saturated steam to the inter-bed cooler, such that the process gas can be cooled to the optimal inlet temperature to the second SO.sub.2 conversion catalyst bed. The heat exchangers are closely linked and have a rather narrow operating window in which the energy balance is in favor of producing sufficient or surplus amounts of saturated steam.
Description of a WSA Plant for the Treatment of Viscose Off-Gas Using the Present Invention
(13) A wet gas sulfuric acid (WSA) plant using the present invention configured for treatment of a CS.sub.2 and H.sub.2S containing lean gas from a viscose fiber production plant is shown in
(14) With respect to the thermal combustion, lean gas bypass, catalytic H.sub.2S and CS.sub.2 oxidation, SO.sub.2 oxidation and H.sub.2SO.sub.4 condensation, the process gas layout of the present invention is largely similar to the traditional layout as described above.
(15) The difference between the traditional layout of the WSA plant and the new layout according to the invention is within the thermal management of the plant.
(16) In the new layout, demineralized water (50) is sent to the de-aerator (51) where oxygen is stripped off using low pressure steam (53). The de-aerated boiler feed water leaves the de-aerator via line (56), and the pressure is increased by the boiler feed water pump (57). The boiler feed water is sent further to the steam drum (62) via line (58). The steam drum is connected to two boilers, namely the process gas cooler (17) and the inter-bed cooler (19) which, in this layout, is configured as a boiler and not as a steam superheater as in the traditional layout. The saturated steam from the steam drum (83) can optionally be throttled before it is sent to battery limit as export steam via line (64).
(17) The main task of the inter-bed cooler is to control the process gas temperature to the downstream catalytic bed and, with a boiler installed, the process gas temperature is controlled by leading a fraction of the hot process gas around the boiler via line (85).
(18) However, since the temperature difference between the process gas passing through the boiler (19) and the bypassed gas (85) can be very large, the performance of the downstream second SO.sub.2 converter bed will decrease if the temperature stratification becomes too large, even though the average temperature is appropriate. This is due to the fact that on one hand the catalyst used for the SO.sub.2 oxidation is losing activity as the temperature is reduced, and on the other hand the conversion will be limited by equilibrium constraints if the temperature is too high. To prevent this, a mixing arrangement is required to mix the cold process gas coming from the boiler with the hot bypassed process gas.
(19) In the new process layout, the inter-bed cooler is a steam generator (boiler), which can be of the fire tube type as well as of the water tube type. The fire tube boiler will typically have to be positioned outside the SO.sub.2 converter shell, with an increased risk of creating cold spots and consequently condensation and corrosion by sulfuric acid. Due to the thick shell of a fire tube boiler, this boiler option is considered to be uneconomical.
(20) A water tube boiler inside the SO.sub.2 converter shell is the preferred solution because the tubes can be oriented in any position from horizontal to vertical, and moreover the tubes can be bare or finned.
(21) It is preferred to use the same boiler pressure in the inter-bed cooler as in the process gas cooler as this allows for sharing the same steam drum and simplifies the layout of the plant. Special circumstances can favor the use of different steam pressures in the two heat exchangers, but this will require two steam drums or connection to an out-of-boundary-limit steam circuit.
(22) The invention is described further in the examples which follow.
Example 1
(23) In this example, 30,000 Nm.sup.3/h viscose off-gas containing 0.38 vol % CS.sub.2, 0.36 vol % H.sub.2S and ambient air as balance, is treated in a WSA plant as shown in
(24) In this example, the sulfuric acid dew point temperature in the process gas stream (18) at the inlet of the WSA condenser (19) is 238° C. only. Therefore, the inlet temperature to the WSA condenser and also the saturated steam temperature in the steam system has been reduced to 270° C. and 255° C., compared to the maximum values of 290° C. and 263° C., respectively. This provides a minimum 17° C. margin to the sulfuric acid dew point in the inter-bed cooler (15)/inter-bed boiler (19) and process gas cooler (17) and 15° C. temperature approach in the cold end of the process gas cooler (17). The steam pressure corresponding to a saturated steam temperature of 255° C. is 42.2 barg.
(25) The reason for reducing the steam pressure and the inlet temperature to the WSA condenser in this example is to maximize the steam production, and to reduce the cost of the steam system by providing a lower design pressure.
(26) Table 1 below shows the difference in number of heat exchangers in the heat recovery system used to control the process temperatures in the plant. As it can be seen, the number of heat exchangers is reduced from four in the traditional layout to only two in the improved heat recovery system. In addition to that, the heat exchange area in the inter-bed cooler is reduced from 43 m.sup.2 in the traditional layout (case A) to 8.5 m.sup.2 in the new layout (case B). This reduction in heat exchange area is partly due to the improvement in the overall heat transfer coefficient, as boiling water with an almost infinite heat transfer coefficient replaces a lower convective heat transfer coefficient of the saturated/superheated steam. Also, the increased temperature differences in the boiler compared to the steam superheater reduces the required heat transfer area. Additionally, there will be a further cost saving, as the boiler typically is made of carbon steel, whereas the steam superheater is made of a more expensive alloyed steel.
(27) In addition to the reduction in the number of equipment parts and the heat exchanger area, the new layout is much simpler in terms of process control.
(28) The inter-bed boiler now operates independently of the operation of the plant, i.e. the performance of the heat exchanger is not dependent on sufficient production of saturated steam for cooling of the process gas.
(29) This also has the benefit that start-ups can be carried out faster and more smoothly, and the operation of the plant will be much more robust towards changes in operation conditions. As an example, the traditional layout depends on a certain heat of reaction in the catalytic beds in order to produce a sufficient amount of saturated steam for the inter-bed cooler, and this constraint does not exist with the new inter-bed boiler solution. If there is an increase in cooling demand in the inter-bed cooler, e.g. by an increase in temperature out of the first catalytic bed (14), then the increase in cooling ability in the inter-bed cooler (15) must await the production of saturated steam in the process gas cooler (17) and the steam generator (80). Contrary to the simple process control in the improved layout, there is a very high degree of heat integration in the traditional layout because the superheated and saturated steam is used for steam production and preheating of boiler feed water, respectively, in order to provide a sufficient steam flow to the inter-bed cooler (15). So because the BFW preheater (59), the steam generator (80) and the inter-bed cooler (15) are all interdependent, any disturbance occurring in one of these heat exchangers will impact the operation of the whole plant.
(30) The known high degree of heat recovery of the plant is maintained, the difference being that only saturated steam is produced in the new layout, whereas a certain degree of superheating was possible in the traditional layout. If superheated steam export is desired, a dedicated steam superheater can be included and installed anywhere between the combustor outlet and the outlet of the final SO.sub.2 catalyst bed.
(31) The following table illustrates a comparison between a sulfuric acid plant with traditional thermal management (case A) and a sulfuric acid plant with the new simple thermal management layout according to the invention, i.e. using an inter-bed boiler (case B).
(32) TABLE-US-00001 TABLE 1 Case A Case B Number of heat 4 2 ex-changers (TEMA: 2, Cross (Cross flow: 2) flow: 2) Inter bed cooler BFW preheater (59) (15) Steam generator Process gas cooler (80) (17) Inter-bed cooler (15) Process gas cooler (17) Inter-bed cooler 43 m.sup.2 8.5 m.sup.2 heat exchange area (15) Inter-bed cooler 100 30 cost index Process gas duty 2.7 Gcal/h 2.7 Gcal/h Duty transferred 4.1 Gcal/h 2.7 Gcal/h in steam cooling system Duty recirculated 48% 0% in steam system
(33) From the table it is seen that the new layout has lowered the number of heat exchangers from 4 to 2 and reduced the size and cost of the inter-bed cooler significantly. In the traditional layout, 48% extra duty is internally transferred to cool the process gas, whereas in the new layout, no internal transfer/recycle of heat is needed to be able to achieve the desired cooling of the process gas.
Example 2
(34) A further example of the application of the present invention is shown in
(35) Optionally, if NOx emissions need to be reduced, an SCR reactor (113) will be installed and a small amount of ammonia will then be added to the process gas via line (145). In order to ensure sufficient oxygen for the conversion of SO.sub.2 to SO.sub.3 in the SO.sub.2 converter (12) and in order to reduce the sulfuric acid dew point of the process gas, preheated dilution air is added to the process gas via line (146). The diluted process gas (122) then enters the SO.sub.2 converter (12), which in this case is configured with three adiabatic catalytic beds (13, 14 and 124) containing a sulfuric acid catalyst active for the oxidation of SO.sub.2 to SO.sub.3. In the first bed (13), the majority of the SO.sub.2 oxidation takes place, increasing the process gas temperature out of the catalyst bed to 500-550° C. In the first inter-bed cooler (19), the partially converted process gas is cooled before being sent to the second bed (14) for further conversion. The further converted process gas is then sent to the second inter-bed cooler (123), where the process gas is cooled to the third bed (124) inlet temperature. The final SO.sub.2 conversion ensures an overall SO.sub.2 conversion of about 99-99.7%. The process gas is then cooled in the process gas cooler (17). The converted process gas (18) is then sent to the WSA condenser (19) for further cooling to about 100° C., hydration of SO.sub.3 to H.sub.2SO.sub.4 and condensation of the H.sub.2SO.sub.4. The cooling medium for the WSA condenser is ambient air which is compressed in the cooling air blower (33). A fraction (138) of the hot air (35) from the WSA condenser is further compressed in the hot air blower (139) and used as combustion air (141) in the combustor (6) and as dilution air (142). The remaining hot air can be used for boiler feed water preheating in (159) and/or addition to the clean gas from the WSA condenser, which may optionally have been subjected to additional cleaning in e.g. a caustic or hydrogen peroxide scrubber and/or a mist filter (not shown in
(36) The process gas cooling taking place in the waste heat boiler (110), the first and the second inter-bed cooler (19 and 123) and the process gas cooler (17) are by means of steam boilers, preferably water tube boilers. The first and the second inter-bed coolers are both to be configured with a hot process gas bypass (85, 185) and a downstream mixer (not shown) to ensure optimal and uniform inlet temperature for the downstream catalyst beds. All boilers are connected to the steam drum (62) via risers and downcomers (70/71, 81/82, 114/115 and 181/182). Finally, saturated export steam is withdrawn from the steam drum via line (64). In case the steam export is required to be superheated, one of the two inter-bed coolers may be configured as a steam superheater similar to the layout shown in
(37) In this example, the sulfuric acid dew point temperature in the process gas stream (18) at the inlet to the WSA condenser (19) is 263° C. due to a high content of both water and SO.sub.3 vapor. Therefore, the inlet temperature to the WSA condenser and also the saturated steam temperature in the steam system is selected as the maximum values 290° C. and 263° C., respectively. This provides a minimum 12° C. margin to the sulfuric acid dew point in the inter-bed boilers (19, 123) and process gas cooler (17) and 15° C. temperature approach in the cold end of the process gas cooler (17).
(38) In the traditional layout, the inter-bed coolers are steam superheaters, using the saturated steam produced in the waste heat boiler (110) and the final process gas cooler (17). Although the production of saturated steam is higher than in the case with the viscose off-gas (Example 1), the production is not high enough to ensure a simple control of the two inter-bed coolers. Traditionally, the saturated steam is first passed through the second inter-bed cooler for first superheating and then to the first inter-bed cooler for final superheating, each cooler being equipped with a bypass system for control of the process gas temperature. Between the two inter-bed coolers it is necessary to add a steam de-superheater to allow for sufficient cooling of the process gas in the first interbed cooler. The de-superheater is often a compact boiler, producing saturated steam for the steam cooling circuit. The superheated steam leaving the first inter-bed cooler may also be required to pass through a de-superheater to produce more saturated steam for the steam cooling system. In the traditional layout, the internal transfer of heat is only 5% of the total duty (see Table 1 in Example 1 for explanation), which again is reduced to 0% in the new layout of the invention.
(39) The traditional steam cooling system has a very high heat recovery, but also interdependency between the heat exchangers. As the inter-bed coolers need saturated steam to function, the start-up of the plant can be long because the production of saturated steam must balance the need for cooling in the inter-bed coolers.
(40) This complexity and interdependency is eliminated by the introduction of boilers as inter-bed coolers—the control of the process gas temperature to the second and the third catalyst beds being straightforward as the process gas is bypassed and the cooling does not depend on production of steam in other heat exchangers. This also allows for a much faster start-up of the plant.
(41) As in Example 1, the new layout allows the same high heat recovery as the traditional layout with the use of fewer heat exchangers. The inter-bed coolers will require less heat transfer area and the material of construction will be carbon steel as opposed to the higher alloyed steels employed for the traditional heat exchangers.
Example 3
(42) A further example of the application of the present invention is shown in
(43) The process gas cooling taking place in the waste heat boiler (110), the first and the second inter-bed cooler (19 and 123) and the process gas cooler (17) is achieved by means of steam boilers, preferably a fire tube boiler for the waste heat boiler and water tube boilers for the interbed cooler and process gas cooler. The first and the second inter-bed coolers are both to be configured with a hot process gas bypass (85, 185) and a downstream mixer (not shown) to ensure an optimal and uniform inlet temperature to the downstream catalyst beds. All boilers are connected to the steam drum (62) via risers and downcomers (70/71, 81/82, 114/115 and 181/182). In case the steam export is required to be superheated, one of the two inter-bed coolers may be configured as a steam superheater similar to the layout shown in
(44) In this example, the sulfuric acid dew point temperature in the process gas stream (18) at the inlet to the WSA condenser (19) is 260° C. due to a high content of both water and SO.sub.3 vapor. The inlet temperature to the WSA condenser and also the saturated steam temperature in the steam system are selected as 290° C. and 260° C., respectively. This provides a minimum 15° C. margin to the sulfuric acid dew point in the inter-bed boilers (19, 123) and process gas cooler (17) and 15° C. temperature approach in the cold end of the process gas cooler (17).
(45) In this specific layout, the production of saturated steam in the waste heat boiler (110) and the process gas cooler (17) is sufficient for a simple layout of the inter-bed coolers with saturated or superheated steam on the cold side of the heat exchangers, and thus the complexity and interdependency is less in the traditional layout.
(46) However, in the new layout according to the invention, the size and cost of the inter-bed coolers will still be significantly reduced, and the start-up of the plant with the new layout will still be faster.