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Special Report                                                                   Special Report



 *   Secondary/fi nal gas cooling;  value product makes the process more  ing and other purposes in the steel plant.   present as it also takes part in the
 3
 *   Ammonia removal;  profi table.   So, 330-m /THM of COG is available   reaction.
 *   Benzol removal;  for ammonia or methanol synthesis.
 *   Naphthalene removal; and  Water wash process                            For the methanol synthesis reaction
 *   Hydrogen sulphide removal.   This is the simplest and frequently   Based on the Ministry of Steel   with CO and CO , the stoichiometric
                                                                                         2
 used process for ammonia  stripping  Annual Report (2023-24), hot metal   number (Sn) of the syngas feed, which
 These steps are carried  out under  from COG.  The ammonia present in  production in India was 87.045-mt.   is defi ned as ((H  – CO )/(CO + CO ))
                                                                                              2
                                                                                                        2
                                                                                        2
 7-kPa to 15-kPa pressures.  the COG is absorbed using water and  Hence, the total annual gas production   should be: 2 ≤ Sn ≤ 2.1. Following this
 the absorption liquor is then stripped of  would on average be as follows:   ratio, the CO and CO  requirement
                                                                                              2
 A summary of the process for  ammonia in a distillation column using  * BFG – 130,567-mscm;  for the amount  of H  present can be

                                                                                            2
 cleanup are given below(2)(9)(10).   steam. The stream leaving at the top of  * COG – 34,818-mscm; and  calculated.  Methane present in  the

 the stripper is rich in ammonia and can  * LDG – 8,704-mscm.             COG can be separated  by adsorption

 Tar removal  be converted to fertilizer or anhydrous                     using activated carbon and the separated
 Tar is a condensable vapour consist-  ammonia.  The quantity of H  would be   methane can be subjected to steam re-
 2
 ing mainly of  aromatic hydrocarbons   20,991.7-mscm (34,818 mscm x 60.29%)   forming. Steam reforming generates
 ranging from volatile benzene to pitches  Hydrogen sulphide removal  or 1.874-mt.   This is equivalent  to   CO along with H , which can be used
                                                                                         2
 (which are solid at room temperature).   This process is used for deep  de-  50 x 1.874 = 93.71-GW of power. If   for methanol production:  CH  + H O
                                                                                                        2
                                                                                                   4
 Tar can  be removed  as a saleable  sulphurization of steel plant gases.  It  electrolysers  were used for hydrogen    CO + 3H
                                                                                    2
 material that can be further processed in  is generally used after another desul-  production, 93.71-GW would be the
 a tar distillation plant. Around 70% of  phurization process – like alkanolamine  savings in solar PV systems. This is the   The production of ammonia
 the tar is condensed when sprayed with  or Selexol process. In this process, the  potential for H .   requires N  and H  in the ratio of 1:3.
 2
                                                                                   2
                                                                                         2
 liquor. Further, 20%  is removed  at  steel plant gases are passed through a   N   is  obtained  using  suffi cient  quantity
                                                                            2
 the primary cooler and the remaining  bed of zinc oxide (ZnO) at high tempera-  The utilization of these gases would   of BFG, by separating  N  from CO
                                                                                                2
 10% in electrostatic tar precipitators.  tures where  the H S reacts  with ZnO  require  converting  them  to  other  profi t-  and CO . CO and CO  can be used for
                                                                                            2
                                                                                 2
 2
 to produce ZnS.   able chemicals, which in most cases                    methanol production as  COG  alone
 Ammonia removal  require H .  The possibilities  are con-                does not have suffi cient CO for methanol
 2
 Ammonia  removal from COG is  Generation of gases in a steel plant  version to methanol,  ammonia,  and   reaction (Figure 1).
 done mainly using the following three   In a typical steel plant, the quantity  certain  chemicals that can be made
 methods:  of byproduct gases generated per tonne  utilizing  CO or CO  and methanol,   Mass balance
 2
 of hot metal (THM) are(9)(10):   etc.  The  entire  process requires  that   The overall mass balance  for the
 Ammonium sulphate process  *  BFG  –  1,200-2,000-m /THM  the components of steel plant gases be   process is shown in Table-3. The mass
 3
 There can be a few variations in   (average: 1,500-m /THM)  separated,  as required by the process   Fig. 1: Flowchart for methanol and ammonia synthesis from steel plant gases  balance  is calculated  based on the
 3
 this  process, but it basically  involves  * COG – 300-500-m /THM (average  and then reacted to give the desired
 3

 sulphuric acid and COG to be contacted   400-m /THM); and  chemical.   Table-3: Overall mass balance
 3
 to form ammonium sulphate.   *   LDG – 80-150-m /THM (100-m /  COG  COG   Adsorption with   Methanol   Steam   Adsorption with   Ammonia
 3
 3
 THM).  Case 1: Production of methanol and   treated  AC  synthesis reforming      zeolite       synthesis
 Phosam process  ammonia.           Stream 1  Stream 2                       Stream 1  Stream 2
 The process uses  a  solution of   It is also assumed that around 70-m /  Methanol synthesis requires a combi-
 3
 mono-ammonium phosphate for absorbing  THM of COG will  be used for heat-  nation of H  and CO; CO  can be   H 2  198.957  198.957  192.85  6.1  256.67  254.6  1.985
 2
 2
 ammonia, forming di- and tri-phosphate   CO  16.632  16.632  12.5  4.12  120.51         120.51
 salt solution.  The process is reversed   Table-2: Composition of gases produced per tonne of steel  CH  83.523  83.523  83.523
 by stripping with high pressure steam   Component  BFG (m /THM)  Vol%  COG (m /THM)  Vol%  4
 3
 3
 to obtain anhydrous ammonia. An alter-  CO  340.8  22.72  16.632  5.04  CO 2  4.257  4.257  4.257  4.257  4.257
 native is the production of diammonium   CH  0  0  83.523  23.86  N 2  14.718  14.718  14.718  14.718  14.718
 phosphate for fertiliser use.   4  O  0.957  0.957  0.957
 CO 2  317.7  21.18  4.257  1.28  2
 Using the Phosam process, ammonia   N 2  802.5  53.50  14.718  4.46  C H m  10.956  10.956  10.956
         n
 found  in  raw coke  oven  gas  can  be   O  0  0  0.957  0.273  CH OH  72.309
          3
 2
 converted into commercially pure   C H  2.7  0.19  10.956  3.13  H S  1 % vol
 anhydrous ammonia. Compared to   n  m  2
 ammonium sulphate operations, this high-  1,500  330  NH 3  0.5 % vol                              82.327
 176  Chemical Weekly  June 17, 2025  Chemical Weekly  June 17, 2025                                   177
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