C.P.I.

ASSIGNMENT Ammonia removal from coke oven gas

Submitted by -: Akshay Sharma U.S.C.T.(3rd year) 01716101409

Ammonia Removal
Ammonia (NH3) is a by-product of the coking of coal. It is a constituent of the coke oven gas leaving the ovens. The solubility of ammonia in water leads to its presence in the coke battery flushing liquor. Ammonia removal from gas streams remains a universal feature of coke oven by-product plants. The reason for this is that ammonia, in the presence of the other coke oven gas contaminants hydrogen cyanide, hydrogen sulphide, oxygen and water, is extremely corrosive to carbon steel. In former times, an added incentive was the profitable sale of by-products such as ammonium sulphate, anhydrous ammonia and concentrated ammonia solutions. With the possible exception of anhydrous ammonia, the reduced market value of these by-products, especially in the industrialised nations, no longer makes their production profitable. Ammonia removal from liquid streams is performed mainly for environmental reasons.

Ammonia Removal from Coke Oven Gas

The presented used methods for removal of ammonia from coke oven gas are variations of three basic processes. Those are the Ammonium Sulphate process, the Phosam process and the Water Wash process.

a) The Ammonium Sulphate Process

The ammonium sulphate process removes ammonia from the coke oven gas by absorption in a solution of ammonium sulphate and sulphuric acid. The ammonium sulphate produced by the reaction of ammonia with sulphuric acid is recovered by crystallisation. The crystals are then centrifuged, washed and dried. The various ammonium sulphate systems in operation differ in the type of gas/liquor contacting device and the type of crystallisation equipment used. An early and still very commonly used system employs a dip tube extending below the surface of the acid/ammonium sulphate solution in a vessel referred to as a saturator . The solution strength is maintained around 4% acid. Coke oven gas is fed through the dip tube and gas/liquid contact is effected as the gas bubbles up through the solution in the saturator. Acid is continuously added to the saturator. The heat of reaction between ammonia and sulphuric acid causes the evaporation of water into the coke oven gas. The concentration of ammonium sulphate reaches saturation, causing crystals to form directly in the saturator where they are allowed to grow until they are removed from the system. The traditional material of construction for the saturator and all wetted surfaces is lead lined carbon steel. Alloys such as Monel and 316 stainless steel are also used. Brick lining is used to protect the lead lining, which suffers from creep and damage by erosion. The major economic disadvantage with ammonium sulphate processes is the price relationship between sulphuric acid and ammonium sulphate. The sulphuric acid required to make ammonium sulphate can cost up to two times the value of the ammonium sulphate product.

b) The Phosam Process

In the Phosam process, ammonia is selectively absorbed from the coke oven gas by direct contact with an aqueous solution of ammonium phosphate in a 2- stage spray absorption vessel (see Fig 6). The absorption solution actually contains a mixture of the following: phosphoric acid H3PO4, mono ammonium phosphate NH4H2PO4, di-ammonium phosphate (NH4)2HPO4 and triammonium phosphate (NH4)3PO4. The absorption reactions that take place are: H3PO4 + NH3 NH4H2PO4 NH4H2PO4 + NH3 (4)2HPO4 (NH4)2HPO4 + NH3 (4)3PO4 The ammonia absorbed is recovered by steam stripping. This regenerates the absorption solution which is returned to the spray absorber. The steam stripping is performed at high pressure, around 13 bar. The reason for this is that the reversible reactions which liberate the ammonia from solution are favoured by higher temperatures. Therefore by operating at high pressure (and hence higher temperature) the consumption of stripping steam is minimised. The overhead vapours from the stripper are virtually only water vapour and ammonia. These vapours are condensed and then fed to a fractionating column where anhydrous ammonia is recovered as the condensed overhead product .The fractionator bottoms product, mainly water, leaves the system as effluent. The Phosam process can become contaminated by tar and by absorption of acid gases (HCN, H2S and CO2) in the recirculated solution. To remove the tar, a froth flotation device is installed in the solution circuit between the absorber and the stripper. Acid gases are removed by preheating the ammonia rich solution and feeding it into a vessel referred to as a contractor. In this vessel, the preheat causes vaporisation of water and acid gases from the solution. These vapours are vented back to the coke oven gas main and the remaining rich solution is fed to the stripper. A subsequent step to deal with any remaining acid gases and prevent them from contaminating the anhydrous ammonia, is to add sodium hydroxide to the fractionator feed. The sodium hydroxide fixes the acid gas compounds as non-volatile sodium salts which remain in the fractionator bottoms effluent stream. The Phosam process is very efficient, capable of achieving greater than 99% recovery of ammonia from coke oven gas. Other plant configurations are possible in which, for example, aqueous ammonia solution is produced instead of the anhydrous ammonia. Materials of construction are stainless steel for all areas in contact with phosphate solution of aqueous ammonia, and carbon steel for other areas. As in the sulphate process, ammonia present in excess flushing liquor is handled first by distillation, with the vapours being fed to the coke oven gas upstream of the Phosam absorber.

c) The Water Wash Process

One of the simplest and most frequently used methods of removing ammonia from coke oven gas is to absorb it in water. Aqueous absorption liquor is fed counter currently to the flow of coke oven gas in an ammonia washer vessel . The vessel can be designed as a spray type absorber with several liquor respray stages, or as a packed tower The type of packing generally used is vertically arranged expended metal sheets which promote gas/liquor contact but resist playing and fouling. The rich ammonia solution formed, is then fed to a distillation columns where the ammonia is stripped from the aqueous liquor using steam. After stripping, the absorption liquor is cooled and returned to the washer. There is a continuous blowdown of stripped liquor from the circuit which is equivalent to the volume of steam condensed in the stripper column. This blowdown is plant effluent and requires biological effluent treatment to fully remove the residual ammonia. As no chemical reactions are involved, other than the dissolving of ammonia in water, the water wash process is temperature dependent and is most efficient at low coke oven gas temperatures (20-30C). Use of aqueous absorption liquor results in the simultaneous absorption of significant quantities of acid gases (H2S, CO2, HCN) from the coke oven gas. Therefore, the ammonia stripping column is nowadays often constructed of corrosion resistant materials such as titanium and 316 stainless steel, although many plants continue to operate cast iron stills. The presence of fixed ammonia does not influence absorption of free ammonia from the coke oven gas.The fixed ammonia can be removed in the stripping column by the addition of caustic soda. Alternatively, the blowdown stream can be fed to a separate fixed ammonia still. The use of a separate fixed ammonia still avoids the presence of alkali in the recirculating absorption liquor, which can be responsible for forming fixed compounds with acid gases such as hydrogen cyanide and leading to the presence of these compounds in the plant effluent stream.