Patent Application
20110311433
The invention relates to a process for concentration of sulphuric acid. The invention is specifically directed to concentrating a 90-98 wt % hot sulphuric acid to a 95-98.8% concentrated sulphuric acid.
This is especially useful in connection with purification of sulphur containing flue gasses and off-gasses, where sulphur is present as sulphur trioxide and is removed as acid, which is formed by condensation of the sulphur trioxide/water containing gas. This process is called Wet gas Sulphuric Acid process, WSA.
The WSA technology has proven its value in industries like oil refining, metallurgy, petrochemicals production, coking, coal gasification, non-ferrous roasters or smelters, power plants and production of viscose fibers.
It is known to remove sulphur from flue gas or off-gas by oxidising sulphur compounds to sulphur trioxide, and then cool the sulphur trioxide in the presence of the water in the gas to form sulphuric acid, followed by condensation and concentration of the formed acid.
In patent EP 0 844 211 a process for this is disclosed. The condensation takes place in a tower, and the formed sulphuric acid is lead from the bottom of the tower to a concentrator. The heat, which is needed for the concentration process, i.e. evaporation of water, is added by hot air, which is used for stripping out water from the sulphuric acid. However, high temperatures in equipment with sulphuric acid are very demanding for the construction materials.
Another process for concentrating sulphuric acid is described in patent GB 17 158. This process avoids use of hot air by letting the concentration process i.e. evaporation be performed under vacuum.
Removal of sulphur trioxide from off-gases and concentrating a strong sulphuric acid are disclosed by U.S. Pat. No. 6,174,510. The sulphur trioxide is absorbed by a 98.5% sulphuric acid, and it is performed in a rather complex piece of equipment.
As used herein hot sulphuric acid shall unless other temperatures are indicated be construed as sulphuric acid having a temperature above the boiling point of water, i.e. 100° C. at 1 atmosphere.
As used herein dried air shall be construed as air or another gas being treated by a water removal process such as cooling or absorption, to arrive at a humidity below saturation at the operating temperature. Dry air shall be construed as synonymous with dried air, and shall not imply and absolute absence of water.
As used herein warm or hot cooling air shall be construed as the air at the outlet from a cooling system, and may therefore have any temperature.
It is an object of the invention to provide a method and an apparatus for concentrating a 90-98% sulphuric acid under mild conditions for the construction materials, for operation with improved consumption figures, and for obtaining high concentrations of the sulphuric acid.
The invention provides a process and system for production of concentrated sulphuric acid from sulphuric acid by stripping the hot sulphuric acid with dried air. The concentration of the sulphuric acid is 90-98% by weight, and the concentration of the concentrated sulphuric acid is 95-98.8% by weight. The hot sulphuric acid can be above 200° C. The air can be dried in a dehumidifier. The sulphuric acid can be formed by cooling of a gas such as an off-gas comprising a mixture of sulphur trioxide and water and condensing the formed sulphuric acid. The cooling and condensing can take place in an air cooler, and if an absorption dryer is used, it can be regenerated by warm air transferred from the outlet of the air cooler.
Sulphur containing off-gasses are formed by combustion of sulphur containing fuel or as the off-gasses formed in chemical processes, possibly after combustion of offgasses. The sulphur is then present as sulphur dioxide.
After catalytic oxidation of the sulphur dioxide to sulphur trioxide the gas, also containing water, is cooled and sulphuric acid H2SO4 is formed during condensation resulting in 90-98 wt % sulphuric acid.
To further concentrate the sulphuric acid, the water must be stripped off. This evaporation of water requires energy, which is in prior art done by adding heat by stripping with hot air, 450° C.-500° C., resulting in 95-98.8 wt % sulphuric acid.
It has now been found that this concentration can be obtained by stripping with considerably colder air. The air shall in this case be dried, e.g. by passing through a dehumidifier.
In a preferred embodiment of the process, 90-98% hot sulphuric acid is further concentrated to 95-98.8 wt % by flowing down in a stripper with a packed bed in counter current with air at a temperature from ambient temperature to 600° C., this is typically from 20-600° C., preferably from 220-450° C., more preferably 280-320° C. and most preferably 290-310° C. The dried air may contain less than 10 g water/kg air, preferably less than 5 g water/kg air. The air flow may be 0.1-1 Nm3/kg preferably 0.2-0.6 Nm3 air per kg produced concentrated sulphuric acid. The sulphuric acid may come from a storage tank and being pumped through a heater to obtain a temperature above 200° C. A temperature of the sulphuric acid above 200° C., will have the effect of an increase water vapour pressure above the sulphuric acid, and thus and increased stripping of water.
Dried atmospheric air or another gas must be supplied to this stripping process from a system for supplying dried air comprising a dehumidifier
In some cases one or more of the following optional units must also be present in the air stream; an air filter in the event the air is not clean and dust-free, a means of air movement such as a dry air blower in the event the air is not pressurized, and a dry air heater in the event a higher temperature than the supply temperature is required.
The dehumidifier can most conveniently be a desiccant, absorption dehumidifier, and in this case the dehumidifier is regenerated by removing the absorbed water by warm air. Warm air can be generated in a number of ways; some examples are electric heating, heating by steam and by waste heat from other processes.
The temperature of the air to the stripper could be the blower outlet temperature. However, it is preferred that the air from the dehumidifier passes a heater to obtain a temperature of 20-30° C. above the temperature of the sulphuric acid. This means that most often the dry air temperature is 220-450° C. preferably 290-310° C. This temperature is high enough to avoid any risk of mist formation and low enough to not exceed the design temperature of the equipment.
Another embodiment is applicable, when sulphur trioxide containing gas is the raw material, then gas is cooled and the acid condensed in a cooling tower with tubes by cooling air. The condensed acid leaves the air cooler at 200-290° C.
The cooling air having passed the condenser may be appropriate for regeneration of the dehumidifier, and it will furthermore save some energy to use some of the heat content of this warm cooling air. This cooling air having passed the condenser is typically 200-260° C. and after mixing with cold cooling air, it may be introduced as regenerating media in the dehumidifier most often at 120° C. or 160° C.
In this preferred embodiment the condenser and the stripper are built in one and the same column, integrated sulphuric acid column with the stripper part below the condensing part, so the formed acid flows directly down in the packed bed, where the concentration of the sulphuric acid is increased.
In yet another preferred embodiment, sulphuric acid is formed in a separate condensing tower equipped with a number of vertical tubes. The condensed sulphuric acid is then pumped to the top of a stripper, where it passes a bed of packing materials.
The air from the top of the stripper is in this case passed to the gas inlet of the condenser.
Using dried air at a moderate temperature for stripping requires a lower amount of air compared to the use of hot air. Consequently, using dried air has the benefit that the columns can be smaller and more compact, often half the size of columns of prior art.
In all cases it is important to avoid the hot air temperatures of prior art in the towers with strong acid, especially if mal-operation occurs. This may result in hot air flowing through the stripper and back through the condenser if present, and especially the typical condenser has not been designed for the temperature of the hot air of the prior art, i.e. 450-500° C. This is avoided in the disclosed process.
Further, the disclosed process requires less energy for air heating compared to prior art, and all of the energy for dehumidifier regeneration can be provided from waste heat from the condenser in the disclosed process, and still a strength of 95-98.8 wt % sulphuric acid is obtained.
One specific embodiment is shown in
Sulphuric acid in storage tank 30 is transferred by acid feed pump 31 through acid heater 32 in pipe 33 to stripper 10. In stripper 10 the acid is passed downwards through a packed bed 11 in counter current flow with dry air 12. By this, water is removed from the sulphuric acid and leaves the stripper 10 with the humid air 14, while the concentraced sulphuric acid 16 is withdrawn from the bottom of the stripper 10.
The dry air 12 is atmospheric air, which may have passed a dry air filter 20, before it is dried in dehumidifier 21 upstream of dry air blower 22. The air is blown through dry air heater 23, before it is introduced to the stripper 10 at the bottom.
The dehumidifier 21 is most often an absorption dryer such as a desiccant dehumidifier. It is regenerated by the warm cooling air 25.
Another preferred embodiment is shown in
Also in this embodiment, the dry air 12 is atmospheric air, which may have passed a dry air filter 20, before it is dried in dehumidifier 21 upstream a dry air blower 22. The air is blown through dry air heater 23, before it is introduced to the stripper 10 at the bottom.
The dehumidifier 21 is in this embodiment regenerated by the warm cooling air 5 from the condenser part of the integrated sulphuric acid column 15.
Yet another preferred embodiment is shown in
Also in this embodiment this dried air 12 is atmospheric air, which has passed a dry air filter 20, before it is dried in dehumidifier 21 upstream of dry air blower 22. The air is blown through dry air heater 23, before it is introduced to the stripper 10 at the bottom.
The dehumidifier 21 is most often an absorption dryer such as a desiccant dehumidifier. It is regenerated by the warm cooling air 5 having passed the condenser 2.
The concentration process according to the invention is a significant improvement of the WSA process, which will have significant value in the same industries such as oil refining, metallurgy, production of petrochemicals, coking, coal gasification, non-ferrous roasters or smelters, power plants and production of viscose fibers. The WSA plant capacities range from 2,600 to 1,200,000 Nm3/h process gas and up to 1140 MTPD sulphuric acid.
Sulphur trioxide containing off-gas is cooled and the acid is condensed in a condenser and the formed sulphuric acid is transferred to a stripper, where the concentration of the acid increased by stripping with dry air, according to an embodiment corresponding to
The prevailing streams, temperatures, pressures and inlet concentrations are given in Table 1 together with the obtained outlet concentrations.
The results show that the concentration of a 93 wt % H2SO4 is increased by 3.3 wt %.
Sulphur trioxide containing off-gas is cooled and the acid is condensed and the concentration of the formed sulphuric acid is increased in an integrated sulphuric acid column, according to an embodiment corresponding to
In this case the condensed acid is 98 wt %, and easily concentrated to 98.5 wt % by the disclosed process. This is important for example in the refinery industry, where this high concentration for a product is needed.
To concentrate around 5000-5500 kg/h sulphuric acid by the process, according to an embodiment corresponding to
98.5 wt % H2SO4 is obtained both by the disclosed process and by process of the prior art. But it is seen that considerably less air as well as smaller stripper and smaller bed is required by the disclosed process compared to prior art.
In a column with 40 m2 contact area 5415 kg/h sulphuric acid, 97.44 wt %, 260° C., is stripped with 1000 Nm3/h air, in a process according to an embodiment corresponding to
The obtained acid concentrations and temperatures are shown in Table 4 and
These results are also shown in
