Young Innovators Choice Competition - 2012

Report On Conversion of 30kg/day of Oleum by-product into 98% Sulfuric acid

Submitted by Rohit Babel Email id: babelrohit@gmail.com Sandeep N. Gosavi Email id: gosavisn@gmail.com AmoghaVijayadwhaja Email id: v.amogha@gmail.com Contact No. 9967434989 Contact No. 9028539589 Contact No. 8108234995

Team Registration No. CE-0005

ABSTRACT

Oleum is produced in a process as a byproduct and is collected from various points and stored. The amount of oleum produced is 30 kg/day. The oleum collected in the tank in one day is then slowly pumped into a tank containing water and is mixed well with it to produce 98% sulphuric acid. The acid is then let into a storage tank. The heat released during the reaction is removed by circulating cooling water.

Index 1. Problem Statement 2. Conventional approach 3. Process Flow diagram 4. Brief outline of the process 5. Material Balance 6. Energy Balance 7. Safety considerations 8. Material of construction 9. References

1. Problem Statement Oleum is generated in the process as a by-product at the rate of 30 kg/day. The oleum separated at several locations is stored in a tank and pumped out of the system automatically at every one hour interval with the help of compressed air. Suggest a scheme to convert this oleum to 98% sulphuric acid. A process flow diagram with major equipments, mass balance, energy balance and safety interlocks are expected. Also suggest suitable material of construction for this assembly. Work out the capital and operating cost of the scheme.

2. Conventional approach Oleum is converted to sulphuric acid by diluting with acid. However the

reaction is extremely exothermic. Other problems include corrosion, fouling and fuming. The challenges associated are the design of the reactor, heat removal and minimizing the economics of the process. The possible candidates for the reactor to be used are Packed tower Batch reactor Mixer/Agitator

Packed tower Because we are dealing with oleum, the packing to be used should be corrosion resistant. Glass packing, though satisfy this need are extremely delicate and break very easily. Ceramic packing can be used but is very costly. Also, there is a possibility that the fumes of acid may get stuck on the packing.

Batch reactor If we directly mix oleum with water extremely large amount of heat is liberated. The removal of heat is very difficult because we have to use very large amount of cooling water. This is not feasible because the amount of oleum to be diluted is very small when compared to the amount of cooling water.

Mixer/Agitator We have proposed the use of a mixer/agitator assembly in semi-batch mode, where water is taken in the vessel and oleum is slowly pumped into it. This ensures that the heat is released in a controlled manner. The agitator is glasslined. And the heat removed is removed by circulating water in a cooling jacket provided to the vessel.

3. Process Flow Diagram

1. Preparation of 98% sulfuric acid from 30% oleum.

4. Brief Outline Of The Process Oleum (H2S2O7) with 30% of free SO3 is collected in a storage tank with the use of diaphragm pump, from various locations in the plant. 30 kg accumulation of oleum occurs in a day. This oleum is available for conversion to 98% sulfuric acid (H2SO4) which can be sold in the market or used in the process plant.

In short, this oleum is to be diluted to get sulfuric acid. The dilution is actually reaction of free SO3with water. SO3 + H2O H2SO4

Which is a highly exothermic reaction with an enthalpy of H = -871 kJ/kg. So the basic challenge is to control this heat evolved during the operation.

The PFD shown previously gives the schematic for converting this 30% oleum into 98% sulphuric acid. Oleum is sparged into the water in the tank. The process is in semi-batch mode. The required amount of water (calculated from material balance) is already kept in the tank. Oleum is very slowly sparged through this water so that the temperature of the system remains under control.

After the addition is complete, the batch is drained out of the reactor and the sulphuric acid is stored in a storage tank. The entire process is very fast and takes about 6 minutes for the entire oleum to get converted to sulphuric acid.

5. Material Balance We have 30 kg of 30% oleum. That is the amount of free SO3in oleum is 30%. Thus, amount of SO3 = 30 0.3 = 9 kg. According to the stoichiometry SO3 + H2O H2SO4

Assuming that the reaction goes to completion fully because the oleum is introduced slowly into the water, 9 kg of oleum reacts with 2.03 kg of water to form 11.03 kg of acid. Hence total amount of acid = 11.03 + 21 (in feed oleum) = 32.03 kg. If the acid strength is 98%, then,

Therefore water content = 0.65 kg. Hence total amount of water to be taken in the vessel to dilute the oleum to 98% acid = 2.03 + 0.65 = 2.68 kg. For cooling water, assume a flow rate of 0.5 kg/s. Inlet water temperature = 25oC and temperature rise is limited to 10oC. Therefore heat load of cooling water = flow rate specific heat temperature rise = 0.5 4.2 10 = 21 kJ/s. Flow rate of SO3= (heat load / heat of reaction) = (21/871) = 0.02 kg/s. Flow rate of oleum = (heat load / heat of reaction) / oleum strength = (21/871)/0.3 = 0.08 kg/s.

6. Energy Balance Specific heat of water = 4.2 kJ/kgK Specific heat of SO3= 3.83 kJ/kgK Specific heat of sulphuric acid = 1.4435 kJ/kgK Oleum inlet temperature is 40oC (313K). Outlet temperature of acid assumed to be 70oC (343K). Water in the tank is at 27oC (300K). According to stoichiometry 0.02 kg of SO3reacts with 0.005 kg of water to form 0.03 kg of sulphuric acid. Energy input from oleum stream = flow rate specific heat temperature difference = 0.02 3.83 313 = 23.98 kJ/s. Similarly energy input from water of reaction = 0.005 4.2 300 = 6.3 kJ/s. Total energy input = 23.98 + 6.3 = 30.28 kJ/s. Energy of sulphuric acid produced = 0.03 343 1.4435 = 14.85 kJ/s. Heat of reaction = 0.02 871 = 17.42 kJ/s. Total energy out = 32.27 kJ/s. Energy input = Energy out.

7. Safety considerations As the reaction of SO3 with water is highly exothermic (H=871kJ/Kg), if the cooling system fails, a lot of vapour will be generated in the tank. So there is a chance of explosion which needs to be taken care of. For this there is pressure controller which keeps check on the pressure in the vessel. If pressure builds up, the gases are let off to gas scrubber since the vapour of SO 3 and H2O will form

aerosol if let to disperse in the environment as such. It also shuts off oleum inflow.

Sulfuric acid is not flammable; however, under some conditions, it can cause the ignition of other combustible materials if it is allowed to come in contact with these materials. In general, concentrated sulfuric acid should be isolated from organic materials and nitrates, chlorates, carbides, and metallic powders. Hydrogen, a highly flammable, odorless, colorless gas, is generated by the corrosive action of acid on most metals. Consequently, hydrogen can be generated inside a drum or metal storage tank containing sulfuric acid. As hydrogen will form flammable mixtures with air over a wide range of concentrations, ignition sources should not be permitted near storage tanks.

Except when large quantities of water are used to dilute spills (See section on Spill cleanup below), water or alkaline solutions containing water should never be added to sulfuric acid. A violent reaction will take place which may cause spattering to occur. If it is necessary to mix acid and water, the acid should always be slowly and cautiously added to the water.

In selecting valves for sulfuric acid and oleum service, it is necessary to consideracid concentration, temperature, and the service application for the valve.For block valve service, the selections are usually gate valves or plug valves.For temperatures up to about 90C., Alloy 20 valves with Teflon gaskets andpacking are frequently used. However, in the use and manufacture of sulfuricacid, the temperatures may considerably above 95C. andhave necessitated special materials of construction. At least one manufacturer hasdeveloped a gate valve specifically for this type of service which employs an ironalloy, heavy walled section body with Lewmet4 for the discs, seat rings, and

backseat bushings. Normally, plug valves with Teflon soft seats would be satisfactoryat 90 C. and below.

8. Material Of Construction The best material for the construction of the reactor is a high alloy stainless steel. Cast iron is not a particularly strong or tough structural material according to Perrys Chemical Engineering Handbook page 28-29 and is not suitable for the conditions in the reactor because the reactor operates at 375 psia and 435oF (224oC). Carbon steel can not be used because according to Table given below in Plant Design and Economics for Chemical Engineers, oleum is not compatible with carbon steel. Several other alloys such as a nickel-based alloy could be used for the materials and conditions, but would not be the most economic materials. High-alloy stainless steel is the best material for

construction of the reactor.

References: 1. Herrman, Industrial Engineering Chemistry " Volume 33, page 898 (1941). 2. Kirk othmer encyclopedia of chemical technology, Third edition, vol. 22 New York NY, John Wiley & sons,1983 3. Chemical Safety handbook, Southern state chemical, 2002 4. M. Feinberg and P. Ellison. General kinetic bounds on productivity and selectivity in reactor-separator systems of arbitrary design: I. Principles. Ind.Eng. Chem. Res., 40(14):31813194, 2001. 5. R. H. Perry and C. H. Chilton. chemical engineers handbook, 5th ed. Mcgraw-hill (1973). 6. Bichowsky and rossini, thermochemistry of chemical substances (1963). 7. Oleum Safety Data sheet, http://www.rhodia.com/our_company/businesses/documents/Oleum%203 0.pdf