PACKING MATERIAL FOR ABSORPTION TOWER IN SODIUM NITRITE PLANT, RCF EXPERIENCE

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ABSTRACT Rashtriya Chemicals and Fertilizers Ltd., is having Sodium Nitrite / Nitrate Plant at its Trombay Unit. This Plant was commissioned in the year 1974. The Plant is producing Sodium Nitrite @ 12 MT per day and Sodium Nitrate @ 6 MT per day. Sodium Carbonate is one of the raw materials for producing Sodium Nitrite / Nitrate. But, around mid 2008, due to increase in prices of Sodium Carbonate, and reduction in prices of Sodium Nitrite / Nitrate, it was decided to use Sodium Hydroxide solution (20 %) in place of Sodium Carbonate. Besides cost, other factors like ease in handling, and purity of product favored use of Sodium Hydroxide. Some 8 months later after Sodium Hydroxide was introduced, it was observed that the 3 absorption towers used for carrying out the reaction between Sodium Hydroxide and NOx were choked. On opening the Man hole cover, it was found that the Ceramic saddles used as packing material in the tower had crumbled and formed hard cleavages. This problem was referred to the R & D Department. The present paper deals with the R & D findings and the recommendation given regarding suitable MOC for packing material that can be used in the absorption towers.

Rashtriya Chemicals and Fertilizers Ltd., is having Sodium Nitrite / Nitrate Plant at its Trombay Unit. This Plant was commissioned in the year 1974. The Plant is producing Sodium Nitrite @ 12 MT per day and Sodium Nitrate @ 6 MT per day.

Sodium Carbonate is one of the raw materials for producing Sodium Nitrite / Nitrate. But, around mid 2008, due to increase in prices of Sodium Carbonate, and reduction in prices of Sodium Nitrite / Nitrate, it was decided to use Sodium Hydroxide solution (20 %) in place of Sodium Carbonate. Besides cost, other factors like ease in handling, and purity of product favored use of Sodium Hydroxide.

Plant Process:

Sodium Nitrite / Nitrate Plant of RCF was commissioned in the year 1974. This Plant was designed to produce 12 MTPD in the ratio of 1 : 3 (3 MTPD of NaNO2 and 9 MTPD of NaNO3) by scrubbing rich gas with Soda Ash solution. The Plant was later modified to increase the production to 20 MTPD and with a product ratio of 3 : 1 (15 MTPD of NaNO2 and 5 MTPD of NaNO3).

The basic reactions which take place between Soda Ash and Nitrous gases in packed bed Absorption Towers are given below:

Na2CO3 + 2 NO2 = NaNO3 + NaNO2 + CO2 ---------- (I)

Na2CO3 + NO + NO2 = 2 NaNO2 + CO2 ---------- (II)

The reactions which take place between Sodium Hydroxide and Nitrous gases is given below:

NaOH + 2 NO2 = NaNO3 + NaNO2 + H2O ---------- (III)

NaOH + NO + NO2 = 2 NaNO2 + H2O ---------- (IV)

After fractional crystallization and subsequent separation of NaNO2 crystals, the remaining mother liquor is allowed to react with HNO3 in Neutralization Tower according to the following reaction:

8 NaNO2 + 4 HNO3 + O2 = 8 NaNO3 + 4 NO + 2 H2O ---------- (V)

Block Diagram for Sodium Nitrite Section:

SR4 = Soda Ash Soln. Prep. Tank, SR1 = Clean Soln. Storage Tank, C5, C2, C1 = Absorption Towers, SR22 = pH Adjustment Tank, EC1 = Evaporator cum Crystallizer, SR3 = Centrifuge ML Storage Tank.

The Problem:

Some 8 months later after Sodium Hydroxide was introduced, it was observed that there was difficulty in the recycle of solution in the C-5, C-2, and C-1 Absorption Towers that are used for carrying out the reaction between Sodium Hydroxide and NOx. When the Towers were opened, it was seen that a lot of sludge had accumulated in the Tower beds. It was also found that the Ceramic saddles used as packing material in the tower had crumbled and formed hard cleavages. This problem was referred to the R & D Department.

Steps towards Solution:

I. Analysis of dry sludge was carried out in the laboratory

a. Main constituents of Ceramic are, Silica around 73 % Silica, and Al2O3 around 23 %.

b. c.

Silica content in Sodium Carbonate was found to be around 1.2 %. Analysis report of the sludge from the absorption towers showed that it contained around 73 % Silica and around 4.5 % Al2O3.

Conclusion:

It seems that the Ceramic saddles are not resistant to Caustic solution.

II. Effect of Caustic solution, Sodium Carbonate solution, and Nitric acid on Ceramic saddles was studied at 80 C

a. Literature survey says that Ceramic cannot withstand attack by 1 % Sodium Hydroxide above 93 C, and 10

b. c. d. e.

% Sodium Hydroxide above 53 C. Analysis of C-5 Tower solution showed that it contains around 1 % free Caustic at 80 C when the Plant is in normal condition. This value is higher when the Plant conditions are disturbed. Since, the concentration of Caustic solution fed to the Absorption Tower is around 20 % and temperature in the Towers is around 80 C, the Ceramic saddles were kept dipped in 20 % Sodium Hydroxide solution and at 80 C, for 40 hours. Ceramic saddles were kept in around 30 % Sodium Carbonate solution at 80 C, for 40 hours. Ceramic saddles were kept in Nitric Acid (58 % Conc.) at 80 C for 40 hours.

Observations:

1. There is a marked weight loss of around 5 % in the Ceramic saddle kept in Caustic solution.

2. 3.
Conclusion:

No measurable weight loss in Ceramic saddles kept in Sodium Carbonate solution. No measurable weight loss in the Ceramic saddles kept in Nitric Acid (58 % Conc.).

The Ceramic saddles are not resistant to Caustic solution hence cannot be used as Packing Material in the absorption tower. They are suitable for use only if Sodium Carbonate is used as raw material for production of Sodium Nitrite / Nitrate.

III. Study for suitability of Saddles other than Ceramic

Suitability of 1 packing material like Intalox Metallic Tower Packing (IMTP) made of SS, SS Pall Rings, and Pall Rings made of Poly Propylene (PP) was studied by keeping them in three types of solution viz. 20 % Caustic, 58 % Nitric Acid, and C-2 Tower Slurry. The temperature of all these solutions was maintained at around 80 C for 48 hours. After this, all the Packing material was washed with water and dried in oven at 105 C.

Observations:

1. No measurable effect like weight loss or corrosion was observed in case of SS Packing material i.e. IMTP and Pall Rings. 2. In case of PP Pall Rings, minute bubbles were continuously observed on their surface when kept dipped in the above three solutions at 80 C. 3. At the end of the experiment, it was observed that shape of PP Packing Material was distorted.

Conclusion:

1. SS IMTP can be used in the absorption tower of Sodium Nitrite Plant.

2.

PP is not suitable at high temperature of 80 C.

Recommendation:

SS IMTP can be used in place of Ceramic Saddles as Packing Material in the Absorption Tower in Sodium Nitrite Plant.