The anthropogenetic CO2 emanations and planetary heating has alarmed worldly to happen new and better ways to run into the energy demand while cut downing the GHGs. Pakistan is besides badly affected by energy crisis and environmental jobs. Pakistan brick kilns are one of the major fluke gas emanation resources. The intent of this research is to develop a simulation theoretical account to relieve CO2 emanations and utilize it for the production of fertiliser that helps the agribusiness needs and economic system. The widely used MEA dissolver to capture flue gases is replaced by Aqueous Ammonia because the subsequently non merely absorbs all three major acid gases ( CO2, SO2 and NO2 ) to greater extent but besides produces a compound fertiliser from these acid gases which has advantage over other fertilisers and does non pollute the land H2O. It has been found that soaking up efficiency is increased with addition of NH3/CO2 molar ratio. This methodological analysis has been first clip introduced in Pakistan to bring forth a fertiliser from the flue gases of brick kilns. This technique can significantly cut down air pollution and a measure towards sustainability.
The phenomenon of planetary heating has changed its form and converted itself to planetary warning. It is due to non merely the monolithic emanation of GHGs in the ambiance but besides deficiency of appropriate direction system to cut down the monolithic sum of the GHG. GHG chiefly consists of CO2, H2O bluess, methane and last but non least choloroflorocarbon. Harmonizing to the Intergovernmental Panel on Climate Change ( IPCC ) , about three-quarterss of the addition in atmospheric CO2 is attributable to firing fossel fuels. [ IPCC, Climate Change 2001: impacts, version and exposure. Contribution of working group II to the Third Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge: Cambridge University Press ; 2001. ] If the C in all the estimated dodo fuel militias were emitted to the ambiance, the C concentration would lift to more than 5 times pre-industrial degree. [ O'Neill BC, Oppenheimer M. Climate Change: Dangerous Climate impacts and the Kyoto protocol, Science 2002 ; 296 ( 5575 ) :1971-2. ]
With mention to the IPCC anticipation, the ambiance would incorporate up to 570 ppm of CO2 by the terminal of 2100, doing a rise of mean planetary temperature of around 1.9oC and an addition in average sea degree of 3.8 m [ Stewart C, Hessami M.A survey of methods of C dioxide gaining control and sequestration- the sustainability of a photosynthetic bioreactor attack, Energy Convers Manage 2005 ; 46 ; 403-20 ] . Another IPCC studies on CO2 gaining control and storage gives planetary CO2 emanation in 2000 at 23.5GT with about 60 % of this attributed to 7887 beginnings above 100,000 tonne/year including 4942 electrical power Stationss which emitted 10.5GT/year CO2. the staying 40 % emanations were chiefly from transit systems. [ IEA particular study on C dioxide gaining control and storage, IPCC web site: www.ipcc.ch ; 2005 ] .
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Other than power workss and cars brick kilns are besides lending in environmental pollution. Coal and wood are normally employed in the fabrication of bricks in Pakistan. The burning of coal and wood release C dioxide, methane, C atom, azotic oxide and a assortment of manufactured chemicals that do non happen in nature like Chlorofluorocarbons, ozone, C monoxide, non-methane hydrocarbons, ( NMHCs ) and nitrogen oxides [ 2 ] .
Harmonizing to our appraisal there are more than 1000 brick kilns working in the locality of Lahore. The one-year production of bricks is about 46 million per twelvemonth from more than 6000 brick kilns in Pakistan. The emanations from Brick Kiln industry in Pakistan is at scaring degree. It has been estimated that about 533019 dozenss of untreated nursery gases are emitted from these kilns on one-year footing which contribute in assorted environmental jobs can be observed in table 1. [ 2 ] . The tallness of chimney is besides non high plenty because of which the somberness leans downwards to the land, finally fouling the country.
Table 1: CO2 Emissions of states of Pakistan
Green Houses Gases Emission
( tons/year )
Green Houses Gases Emission
Figure 1: Pakistan CO2 emanation ( metric dozenss per capita )
Figure 2: Word CO2 emanation ( metric dozenss per capita )
Emissions from Brick kiln:
The emanations from Brick Kiln industry in Pakistan is at scaring degree. The values of GHGs release calculated from the up matching to 6000 brick units established in the state are 139600, 19600, 495200, 2100, 360, 17 and 540 T severally for entire C ( C ) , C dioxide ( CO ) , C dioxide ( CO2 ) , methane CH4, azotic oxide ( NO ) , nitrogen dioxide ( N2O ) and NOx. It is apparent that GHGs emanations are dominated by C dioxide ( CO2 ) followed by CO and other non- CO2 gases. Projected parts of GHGs from the Punjab state to the state 's entire emanations are highest which can be observed in the Table 1. [ 2 ] .
Environmental issues due to emanations of pollutants from burning of fossil fuels have turned into planetary jobs, every bit good as air toxics and nursery gases ( GHGs ) . The usage of fossil fuels for energy contributes to a figure of environmental jobs globally. Harmonizing to the Intergovernmental Panel on Climate Change ( IPCC ) [ 1 ] , about three-quarterss of the addition in atmospheric CO2 is attributable to firing fossil fuels. Table 2 shows the harmful pollutants released into the ambiance from combustion of fossil fuels. If the C in all of the estimated dodo fuel militias were emitted to the ambiance, the C concentration would lift to more than 5 times pre-industrial degrees [ 2 ] .
Table 2: Fossil fuel emanation degrees ( pounds/billion BTU of energy input )
Surveies have shown that increased GHG degrees in ambiance are believed to do planetary heating. Among these GHGs, CO2 makes up a high proportion in regard of its sum nowadays in the ambiance, lending 60 per centum of planetary heating effects [ 3 ] .
World Consumption of Fertilizer
World fertiliser ingestion increased exponentially in the period 1950- 1990. This growing was spurred by the rise in nutrient demand by increasing universe population. Achieving higher production given the same sum of land can be done through three ways.
Turning more land into cultivable land through better irrigation
Using High Yielding Seeds ( HYS )
Using fertilisers to better dirt content
Improvement in dirt content is the most convenient and often followed method. Furthermore, it has gained widespread usage as nutrient demand rises.
The exponential growing in universe fertiliser ingestion experienced a brief downswing in the early 1990 's due to the prostration of fertiliser ingestion in the states of cardinal Europe and the Former Soviet Union, following structural alterations and economic jobs. However station that brief downswing, growing in fertiliser ingestion is once more on the rise and rapid growing is expected to go on in the hereafter. Harmonizing to IFA estimations, the universe fertiliser ingestion is expected to make 199.2mntpa in 2030 from 174.7mntpa in 2015.
Figure 3: World Fertilizer Consumption
Measure towards Sustainability
It is clear that CO2 is the chief constituent that is present in surplus more than other pollutants and fouling the environment. To maintain the environment clean such techniques must be employed that non merely capture the CO2 and other gases and besides utilize them to bring forth a valuable merchandise from these flue gases. This thing will assist in economic system and maintain the environment clean and finally capturing and transition of CO2 from flue gases into a valuable fertiliser ( NH4HCO3 ) is so the first measure towards sustainability.
The Aqueous ammonium hydroxide is used as a dissolver to capture the fluke gases breathing from the brick kiln which non merely captures CO2, but besides SO2 and NOx. The ammonia solution after soaking up was found to incorporate ammonium hydrogen carbonate [ NH4HCO3 ] , ammonium sulphate [ ( NH4 ) 2SO4 ] , and ammonium nitrate [ NH4NO3 ] , which comprise a compound fertiliser
Figure 4: the fluke gases CO2, SO2 and NOx from the stack of brick kiln are breathing. The reaction of aqueous ammonium hydroxide with CO2 non merely captures CO2 but besides give a by-product ; ammonium hydrogen carbonate ( NH4HCO3 ) used a fertiliser
Absorption ability of Aqueous Ammonia Vs MEA
Amine soaking up engineering
The soaking up engineering which uses amine solution ( MEA ) is being used in natural gas industry for 60 old ages and is considered as a mature engineering. Natural gas industry utilizes MEA to absorb CO2 from natural gas. The remotion of CO2 from burning fluke gas can be done by a figure of commercial MEA soaking up processes. In an absorbent, the MEA solution is allowed to hold a contact with fluke gas which consequences in the soaking up of CO2. When used in a power works, CO2 is entrapped by the dissolver while the fluke gas is bubbled through the dissolver in a jammed absorber column. Subsequently the captive CO2 is stripped off of the dissolver by counter fluxing steam at 100 to 200 grade Celsius in a regenerator unit. CO2 watercourse is concentrated ( up to 99 % ) due to the vaporization of H2O bluess and this watercourse can subsequently be compressed for commercial applications or storage. The procedure is economically hapless as it calls for a big equipment and intensive energy input. Recycle rate of CO2 for MEA is 98 % : The basic reaction for this procedure is:
Disadvantages of MEA procedure
MEA procedure bears some defects which are:
1. Loading capacity of CO2 is little
2. Equipments confronts high corrosion rates
3. High absorptive make-up rate is generated by amine debasement chiefly because of SO2, NO2, HCl, HF and O in fluke gas
4. Energy ingestion is really high particularly during high temperature absorbent regeneration
When the CO2 is entrapped from coal or crude oil derived burning fluke gas, hints of sulphur dioxide should besides be removed to avoid debasement of MEA by SO2 and O meanwhile irreversible debasement merchandises are constituted. The cost of MEA procedure is high on history of debasement even if all of the SO2 is removed from the fluke gas by using a desulphurization unit. Oxides of N should besides be dispatched organize the fluke gas to maintain up the emanation bounds.
Figure 5: Degradation MEA by CO2 and O2
The cost of MEA make-up is high because of debasement, even after most of the SO2 is removed from the fluke gas in an upstream fluke gas desulphurization unit. NOx must besides be finally removed from the fluke gas before it is discharged into the air in order to run into present and future gaseous emanation bounds.
Advantages of Aqueous Ammonia over MEA
Replacement of widely used MEA procedure by individual Aqua Ammonia procedure can ensue in the gaining control of all three major acid gases along with HCl and HF which might be in the fluke gas. Since emanations of SO2 and NOx must maintain up certain emanation bounds, a individual procedure is more than plenty to cut down the capital cost by capturing all the acid gases and besides simplify the complexness of emanation control system. Presently there is no emanation bound on CO2 but clip is non far off when it will besides hold a restricted emanation bound. Sulpher dioxide and O in flue gases can bring on equipment corrosion ; the Aqua Ammonia Process can acquire over this job by cut downing absorptive make-up rate. Another advantage of the Aqua Ammonia procedure over the MEA procedure is that the energy demand for absorptive regeneration is predicted to be really low. Beforehand it was approximated that thermic energy ingestion for CO2 regeneration utilizing the Aqua Ammonia Process could be at least 75 % less than the MEA procedure. Many other economical grounds are besides at that place to back up the ammonium hydroxide procedure
The profitable by-products, ammonium hydrogen carbonate ( NH4HCO3 ) ammonium sulphate ( ( NH4 ) 2SO4 ) and ammonium nitrate ( NH4NO3 ) are produced, used as a fertiliser
Advantage of production of NH4HCO3
China had been preferring ammonium carbonate as a N fertiliser for about 30 old ages. It is already elaborated that when ammonium carbonate is used as a nitrogen fertiliser deep in the dirt its action of work is merely similar urea and ammonium sulfate. As we know that carbonates react with alkalic Earth minerals ( Ca, Mg ) ensuing in the formation of carbonated minerals. Excessive usage of land H2O may do high degrees of alkaline minerals in dirts as in the western United States ; the hydrogen carbonate from ammonium carbonate non merely neutralizes alkalic species but besides deoxidizes salt into stable compounds like H2O and Ca carbonate.
Solid merchandises like CaCO3 are a absolutely stable signifier of cloistered CO2 ( Fig. ) .
Furthermore, dirt had a capableness to move as a engagement stuff which held back NH4+ but allow HCO3- dribble down with rainfalls or irrigation to land H2O which was already enriched with alkalic minerals Ca2+ . Consequently carbonates reacted with alkalic minerals in land H2O ensuing in the deposition of carbonated minerals in the undersoil Earth bed ( fig. 5A ) . Dirt atoms are negatively charged therefore it attracts positively charged ions but repel negative ions due to its higher affinity for positively charged species ( NH4+ ) as compared to negatively charged species ( HCO3- ) .
There upon when ammonium nitrate is used as a fertiliser, NO3- over flows with H2O which non merely consequences in the want of the fertiliser but besides taint of land H2O. Carbonates are non as unsafe species as nitrates because those do non do wellness jobs therefore NH4HCO3 and ( NH2 ) 2CO are preferred fertilisers. Groundwater motion takes carbonates to the Earth subsurface every bit deep as 500 to 1000 m where they deposits as carbonated minerals
Figure 7: Loss of fertiliser and taint of land H2O by utilizing NH4NO3
It is obvious that use of NH4NO3 as fertiliser contaminates the land H2O and NO3- is easy run off where as when NH4HCO3 is used as a fertiliser could cut down the job of NO3- overflow and does non pollute the land H2O.
Aqueous Ammonia Procedure
It has been proposed that the widely utilised MEA procedure is replaced with aqueous ammonium hydroxide procedure to capture all three major acid gases ( SO2, NOx, CO2 ) plus HCl and HF, which may co-exist in the fluke gas. Since SO2 and NOx emanations must stay by with certain emanation bounds, a individual procedure to capture all acidic gases is expected to cut down the sum cost and complexness of emanation control systems. Unlike the MEA procedure, the Aqua Ammonia Process ( AAP ) is non expected to hold absorptive debasement jobs that are caused by sulfur dioxide and O in fluke gas nor is it expected to do equipment corrosion. The application of ammonium hydroxide for coincident decrease of SO2, NOx and quicksilver has besides been reported [ 31 ] .
Different theoretical accounts and methods have been proposed and tested. In our theoretical account, we have chosen Aqueous ammonium hydroxide as the dissolver. The theoretical account was developed on HYSYS 3.2. General NRTL was selected as the fluid bundle. This unstable bundle is rather various and it non merely accommodates the belongingss of our system constituents but besides the aqueous and assorted solvent systems. The flow-sheet of our theoretical account is shown in Fig. 3
Flue gas enters the absorber from the underside to the top through the absorber where interacts in counter-clock manner with aqueous ammonium hydroxide dissolver ( NH3+H2O )
Table 3: Flue gas composing from brick kiln
The procedure of soaking up of CO2 by aqueous ammonium hydroxide involves a complex chemical gas-liquid reaction [ 1 ] , whose general chemical reaction look follows:
NH3+H2O+CO2>NH4HCO3 ( 1 )
In fact, there are a series of in-between reaction procedures incorporated:
NH3+CO2>NH2COONH4 ( 2 )
NH2COONH4 hydrolyzes into NH4HCO3:
NH2COONH4+H2O>NH4HCO3+NH3 ( 3 )
Besides, ammonium hydroxides can respond with H2O to make NH4OH:
NH3+H2O>NH4OH ( 4 )
NH4HCO3 produced by hydrolytic reaction will respond with NH4OH to make ( NH4 ) 2CO3:
NH4HCO3+NH4OH> ( NH4 ) 2CO3 ( 5 )
( NH4 ) 2CO3 absorbs CO2 and creates NH4HCO3
( NH4 ) 2CO3+H2O+CO2>2NH4HCO3 ( 6 )
Spraying aqueous ammonium hydroxide into fluke gas non merely captures CO2 but besides absorbs hints of SOx and NOx from the fluke gas in conformity with the undermentioned chemical equations:
NOx+SOx+H2O>HNO3+H2SO4 ( 7 )
HNO3+H2SO4+NH3>NH4NO3+ ( NH4 ) 2SO4 ( 8 )
The merchandise formed ammonium hydrogen carbonate ( NH4HCO3 ) has been used as a N fertiliser in China for over 30 old ages. It has been good demonstrated that when NH4HCO3 is placed into deep dirt, its nitrogen fertilisation consequence on harvests is similar to that of other N fertilisers, such as ( NH4 ) 2SO4 and urea.
The intent of this work is to relieve the emanation of CO2 from the selected brick kiln, as this gas is among the major perpetrators doing green-house consequence which has finally resulted in drastic and black conditions alterations and temperature-rise to alarming degrees across the Earth. Each twelvemonth the add-on of Carbon dioxide entirely from the brick industry of Pakistan is 35072.65. Gas soaking up has so far been the most utile and advantageous technique which has been covered good in the subdivision station C techniques.
The CO2 soaking up rate surveies were performed in an absorber in dynamic simulation environment on hysys 3.2. shown in Figure 3. The temperature of gases breathing from top of the brick kilns is in the scope of 120 to 150 & A ; deg ; C. The composing of the flue gasses were found utilizing industrial burning and emanation analyser ( E8500, USA ) which is shown in Table 2. Aqueous Ammonia solution is passed through a ice chest in order to diminish the temperature of aqueous ammonium hydroxide temperature, as it gives best consequence at low temperature, introduced from top of the column through valve. The fluke gas is introduced through from the underside of an absorber through a pump that increases its flow rate. In absorber counter flow soaking up takes topographic point and as a consequence, most of the CO2, SOx and NOx are absorbed and a by-product, NH4HCO3, is produced, which is widely used as fertiliser.
Figure 8: Procedure flow sheet
In our Hysys theoretical account we selected an absorber for the soaking up of flue gases. We used different temperature force per unit area conditions for absorber in order to the happen the best soaking up efficiency and cipher the no. of phases. We found that after nine plates the soaking up efficiency is decreased as shown in graph, and maximal soaking up is achieved utilizing aqueous ammonium hydroxide in an absorber of nine home bases.
Figure 9: No of phases Vs mole fraction of CO2 absorbed
In our HYSYS theoretical account, we varied different parametric quantities ( i.e. Temperature, Pressure, Flow-rate, Aqueous Ammonia concentration etc. ) and examined the resulting per centum of CO2 absorbed.
Consequences and Discussion
The rate of soaking up is affected by variables such as temperature, force per unit area, flow-rate, solvent per centum etc. all these variables were manipulated to analyze their consequence on soaking up with the aid of ensuing tabular arraies and tendencies. The consequences of all these parametric alterations are discussed one by one.
Consequence of Flow rate on CO2 Absorption:
The consequences obtained by simulation of our HYSYS theoretical account show understanding with the standard findings that there is addition in soaking up with that of addition in flow rate. In our HYSYS theoretical account, we used different flow-rates and it has been found that soaking up efficiency is increased with addition of NH3/CO2 molar ratio as shown in Fig. At about a NH3/CO2 molar ratio of approximately 1.5, the highest CO2 soaking up efficiency was measured at approximately 97 % and 100 % for instance of NOx and SOx. In our simulation theoretical account at 230kgmole/hr the maximal soaking up of 97 % of CO2 is observed. At high flow rate i.e. after 230 kilogram mol/hr the consequence of flow rate on soaking up does non demo the same increasing tendency. Model with different fluctuation of temperature was simulated but here the coincident consequence of flow rate between 20 & A ; deg ; C to 30 & A ; deg ; C on soaking up of CO2 have been shown
Figure 10: Molar ratio of NH3/CO2 Vs CO2 Absorbed %
Figure 11: Consequence of flow rate of Aq.NH3 on soaking up of CO2
Consequence of Temperature on CO2 Absorption:
It is a good known fact that temperature is reciprocally related to the rate of soaking up, our simulation theoretical account besides gives the correspondent consequences. The system temperature was varied from 15 & A ; deg ; C to 40 & A ; deg ; C with different solvent per centum ( 10.5 % , 14 % and 20 % ) and there was a grade lessening in soaking up rate with the increasing temperature and addition in soaking up with lessening in temperature. The ensuing graph is shown.
Figure 10: Consequence of Temperature on CO2 soaking up
Consequence of NH3 concentration in solution on soaking up rate
The effects of ammonia concentration on CO2 soaking up rate are shown in graph. As the CO2 soaking up reaction progresses, the rates are higher for the solutions with higher ammonium hydroxide concentrations.
As expected, CO2 took longer to divide through the solutions holding higher ammonia concentration. For overall absorptive of CO2, the information forms indicate out that it is more advantageous to utilize a higher concentration ammonia solution as CO2 absorbent. The decisions are the same at all three reaction temperatures. By utilizing 20 % AA at 15 & A ; deg ; C 96 % maximal soaking up is observed. Therefore 20 % AA solution was selected as the optimal solution.
In this work, a theoretical account has been developed and simulated, which aims at the control of CO2 gas which is continuously come ining to the environment from the brick industry in Pakistan and bring forth a fertiliser from the flue gases. It is for the first clip that the brick industry in Pakistan has been analyzed with this position that by spraying aqueous ammonium hydroxide into existent fluke gas produced by a brick kiln can non merely gaining control CO2 but besides absorb SO2 and NOx from the fluke gas and specially gives a compound fertiliser as a by-product.
Presently, there is merely one known commercial procedure that uses ammonium hydroxide to at the same time take SO2 and NOx from fluke gas within one reactor and bring forth assorted ammonium sulfate and nitrate fertiliser
The soaking up efficiency of CO2, SO2, and NOx in existent fluke gas from a coal-burning installation varies depending on the reaction conditions. The soaking up efficiency of CO2 and SO2 was found to increase with an addition in the concentration of aqueous ammonium hydroxide. Over the NH3/CO2 molar ratio of 1 to 1.5 that was tested, and maximum the CO2 gaining control efficiency was measured at 1.5 is 97 % .
The aqueous ammonium hydroxide soaking up solution was found to incorporate a assorted crystalline of ammonium hydrogen carbonate [ NH4HCO3 ] , ammonium sulphate [ ( NH4 ) 2SO4 ] , and ammonium nitrate [ NH4NO3theiˆ ] chief constituents of a compound fertiliser. The captive CO2 in the aqueous ammonium hydroxide solution is in the signifier of HCO3 - and CO3 -2. For a certain molar ratio of NH3/CO2, there is a balanced concentration of HCO3 - and CO3 -2 in the assorted ammonia solution. By spraying the assorted ammonia solution into flue gas incorporating CO2, higher NH4HCO3 content ( higher HCO3 - concentration ) in assorted solution can be obtained.
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