Two mark Questions and Answers 1. What are the different verities of coal? How do you rank them in the order of Increasing calorific value? (or) Write briefly on the ranking of coal. (Dec 2006).
There are five different verities of coal ranked based on their quality and degree of maturity.
Calorific value of the coal increases from left to right. 2. What is coalification (or) metamorphrism of coal? The process of conversion (or alternation) of vegetable matter to anthracite is called coalification or metamorphism of coal. 3. What is the significance of volatile matter in coal? High percentage of volatile matter is undesirable because a) It reduces the calorific value of coal. b) Large proportion of fuel on heating will distill over as vapour, which escapes out unburnt, c) Coal with high percentage of volatile matter burns with a long Flame with high smoke, d) Coal containing high percentage of volatile matter do not coke well. 4. What is carbonisation? The process of heating of coal in absence of air at high temperatures to produce coke, tar and coal gas is called carbonisation. 5. Distinguish between proximate analysis and ultimate analysis. (Coim. A.U. July 2009) Sl. No Proximate analysis Ultimate analysis 1. It means finding out the weight percentages of moisture, volatile matter, fixed carbon and ash in coal. It means finding out the weight percentages of carbon, hydrogen,nitrogen, oxygen and sulphur of pure coal free from moisture and other inorganic constituents in coal 2. It gives approximate composition of the main constituents of coal. It gives the elementary constituents of coal.
6. What is meant by the term Fixed Carbon? Fixed carbon is the pure carbon present in coal. Higher the fixed carbon content of the coal, higher will be its calorific value.
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7. What is carbonization of coal? (Or) What is metallurgical coke? When bituminous coal is heated strongly in the absence of air, the volatile matter escapes out and the mass becomes hard, strong, porous and coherent which is called Metallurgical Coke. This process is called carbonization. 8. What is the difference between caking coals and coking coals? (A.U. Dec 2012) When coals are strongly heated then the mass becomes soft, plastic and fuses to give a coherent mass. Such type of coals are called caking coals. But, if the mass so produced is hard, porous, and strong then the coals are called coking coals. Coking coals possess lower volatile matter and are used for the manufacture of metallurgical coke. 9. How is coke superior to coal? (Or) Distinguish between coal and coke. (Coim A.U.2011) (i) Coke is stronger and more porous than coal. (ii) Coke contains lesser amount of sulphur than coal. (iii) Coke does not contain much volatile matter. (iv) Coke has higher calorific value than coal. (v) Coke burns with small flame without smoke. 10. What are characteristics of metallurgical coke? (i) Purity: Low moisture and ash content are desirable in metallurgical coke. It must contain minimum percentage of phosphorous and sulpur. (ii) Porosity: High porosity is desirable to obtain high rates of combustion. (iii) Strength: The coke should be hard and strong. (iv) Calorific value: The calorific value of coke should be high. 11. What are the advantages of Otto-Hoffmans process? 1. Valuable by products like ammonia, coal gas, naphthalene etc., are recovered. 2. The carbonization time is less. 3. Heating is done externally by producer gas.
12. What is meant by refining of petroleum? (TCY A.U. July, Dec 2009) The process involves removal of impurities and separation of various fractions on the basis of their boiling points from petroleum. 3
13. Define cracking. What is the necessity of cracking of petroleum fractions of higher boiling points? The process of decomposition of less volatile heavier compounds into highly volatile lower useful fractions by the application of heat and pressure or by using catalysts is known as cracking. Crude oil on distillation yields only 16-20% gasoline. This is known as straight run petrol. It contains mainly straight chain paraffins. Usually straight chain hydrocarbons ignite readily and more rapidly than any other hydrocarbons and hence it produces knocking in SI engines. To improve the yield and quality in terms of antiknock properties, higher fractions are cracked to produce high quality gasoline. 14. What is meant by hydrogenation of coal? (or) What do you mean by synthetic petrol? Give a suitable reaction. (Coim. Dec 2011). Conversion of solid coal into liquid petrol by heating the coal with hydrogen at high pressure and high temperature is called hydrogenation. By method the petrol can be synthesized. 15. What is the cause of knocking in internal combustion engine? Name a commonly used antiknock compound?
Knocking is a kind of explosion due to rapid pressure rise occurring in petrol engine. This can be reduced by the addition of TEL (Tetra Ethyl Lead).
16. Difference between knocking in SI engine and CI engine. In SI engine, knocking is due to pre ignition In CI engine, knocking is due to ignition delay. 17. Define octane number of petrol. How can it be improved? (Or) What is leaded petrol? Octane number is defined as the percentage of isooctane in isoooctane-n-heptane mixture, which matches same amount of knocking as the standard binary mixtures when tested in standard engine and standard conditions Octane number of petrol is improved by adding additives like tetra ethyl lead, TEL. Petrol to which TEL is added is called leaded petrol.
18. Define cetane number (or) cetane rating of a diesel oil? How can it be improved? (Dec 2006) Cetane number is defined as, the percentage of cetane present in a mixture of cetane and methyl naphthalene. The cetane number of diesel oil can be improved by adding dopes like Ethyl nitrate. 4
19. How will you improve the anti-knocking characteristics of diesel? (Dec 2006) Antiknocking characteristics of diesel can be improved by increasing n- Cetane (hexa decane) value of the fuel. Cetane value can be increased by adding dopes like ethyl nitrate, Iso-amyl nitrate. 20. What is leaded petrol? Give its significance in automobiles. (Dec 2006) When the petrol is mixed with Tetra Ethyl Lead (TEL), it is called leaded petrol. Significance: Knocking in petrol engine is minimized. 21. Why are gaseous fuels preferred over other kinds of fuels? (i)Calorific value is generally higher than solid and liquid fuels. (ii)Neither ash nor smoke is produced (iii)They need lesser amount of air for complete combustion.
22. Give the composition of LPG and water gas.
(i). Liquefied Petroleum Gas (LPG) n-Butane 70% Isobutane 17% n-Propane 11% Rest - Ethane and Butylene (ii). Water gas Hydrogen 48% Carbon Monoxide 44% Rest CO 2 N 2 , Methane 23. Water gas is superior to producer gas. How? (i) It has higher calorific value (2800 kcals./m 3 ) than producer gas. (ii)It is good source of hydrogen (contains about 48% of hydrogen). So water gas can be used for the manufacture of Ammonia. (iii)Since water gas contains about 48% of hydrogen,it can be used as reducing agent in metallurgical industries. (iv) Water can be used for the manufacture of synthetic petrol. 24. What is gobar gas? State its uses. It mainly consists of methane. It is obtained by fermentation of gobar (dung) in absence of air. It is used as a domestic fuel in villages for domestic heating and small pump running. 25. Mention the significance of flue gas analysis. 5
Flue gas analysis gives an idea about the complete or incomplete combustion process. The presence of a high percentage of CO in the flue gas shows incomplete combustion of the fuel and also indicates short supply of oxygen. If the flue gas contains considerable amount of oxygen indicates an excess supply of oxygen and the possibility of complete combustion. 26. What is meant by combustion of fuels? Combustion is a process of rapid exothermic oxidation, in which a fuel burns in the presence of oxygen with the evolution of heat and light. 27. Define calorific value of a fuel. The calorific value of a fuel is defined as the total amount of heat liberated, when a unit mass of fuel is burnt completely. 28. Distinguish between GCV and NCV. (J une 2007, Dec 2005, J une 2006) Gross or Higher Calorific Value (GCV): The total heart generated when a unit quantity of fuel is completely burnt and the products of combustion are cooled to room temperature. Net or Lower Calorific Value (LCV): The net heart produced when a unit quantity of fuel is completely burnt and the products of combustion are allowed to escape. 29. Give the Dulongs formula for the calculation of GCV and NCV. GCV = 1/100 [8080 C +34500 (H-O/8) +2240 S ] k.cal/kg NCV = [HCV 9/100 H X 587] k.cal/kg.
Important big questions with Answer 1. Explain the proximate analysis coal Proximate Analysis It involves the determination of percentage of 1. Moisture content. 2. Volatile matter. 3. Ash content 4. Fixed carbon in coal. 1. Moisture Content 6
About 1 gm of powdered air-dried coal sample is taken in a crusible, and is heated at 100 to 105C in an electric hot-air oven for 1 hour. The loss in weight of the sample is found out and the % of moisture is calculated as % of moisture in coal =
2. Volatile matter After the analysis of moisture content the crusible with residual coal sample is covered with a lid, and is heated at 950 20C for 7 minutes in a muffle furnace. The loss in weight of the sample is found out and the % of volatile matter is calculated as % of volatile matter in coal = 3. Ash content After the analysis of volatile matter, the crusible with residual coal sample is heated without lid at 700 50C for 12 an hour in a muffle furnace. The loss in weight of the sample is found out and the % of ash content is calculated as % of ash content in coal =
4. Fixed carbon It is determined by subtracting the sum total of moisture, volatile and ash contents from 100. % of fixed carbon in coal = 100 % of (moisture content + volatile matter + ash content) ---------------------------------------------------------------------- 2. How to estimate the percentage of carbon and hydrogen in coal by ultimate analysis? Estimation of carbon and hydrogen contents A known amount of the coal sample is burnt in a current of O 2 in a combustion apparatus. The carbon and hydrogen, present in the coal sample, are converted into CO 2 and H 2 O respectively according to the following equations. Loss in weight of the coal X 100 weight of air dried coal Loss in weight of the coal X 100 weight of air dried coal Weight of ash formed X 100 Weight of air dried coal 7
C + O 2 > CO 2
H 2 + 1/2 O 2 > H 2 O The liberated CO 2 and H 2 O vapours are absorbed respectively in KOH and anhydrous CaCl 2
tubes of known weights. The increase in weight of KOH tube is due to the formation of CO 2
while increase in weight of CaCl2 tube is due to the formation of H 2 O. From the weights of CO 2
and H 2 O formed, the % of carbon and hydrogen present in the coal can be calculated as follows. Calculations 2KOH + CO 2 ------> K 2 CO 3 +H 2 O CaCl 2 +7H 2 O ------> CaCl 2 .7H 2 O Let m = weight of the coal sample taken. x = increase in weight of KOH tube. y = increase in weight of CaCl 2 tube. (a) % of carbon C + O 2 > CO 2
12 44
44 gms of CO 2 contains, 12 grams of carbon Therefore x gms of CO 2 contains = So, m gms of coal contains = 100 gms of of coal contains = (or) % of carbon in coal =
(b) % of hydrogen 12 x gms of carbon 44
12 x gms of carbon 44
12 x 100 gms of carbon 44 m
Increase in weight of KOH tube 12 100 Weight of coal sample taken 44 8
H 2 + 1/2 O 2 > H 2 O 2 18
18 gms of water contains 2 gms of hydrogen Therefore y gms of H 2 O contains =
m gms of coal contains =
100 gms of coal contains =
So, the percentage of hydrogen in coal =
(or)
% of hydrogen in coal =
3. Describe the manufacture of gasoline by Fischer-Tropsch method Fischer-Tropsch process (indirect method for the manufacture of gasoline) In this process coal is first converted into coke. Then water gas (CO + H2) is produced by passing steam over red hot coke. 2 y gms of hydrogen 18
2 y gms of hydrogen 18
2 y 100 gms of hydrogen 18 m
2 y 100 gms of hydrogen 18 m
Increase in weight of CaCl 2 tube 2 100 Weight of coal sample taken 18 9
In this process coal is first converted into coke. Then water gas (CO + H2) is produced by passing steam over red hot coke. C + H 2 O ------ CO + H 2
(Coke) (Steam) (Water gas)
The water gas is mixed with hydrogen and the mixture is purified by passing through Fe 2 O 3 (to remove H 2 S) and then into a mixture of Fe 2 O 3 + Na 2 CO 3 (to remove organic sulphur compounds). The purified gas is compressed to 5 to 25 atm and then led through a converter, which is maintained at a temperature of 200 300C. The converter is provided with a catalyst bed consisting of a mixture of 100 parts cobalt, 5 parts thoria, 8 parts magnesia and 200 parts keiselghur earth. A mixture of saturated and unsaturated hydrocarbon is produced as a result of polymerisation nCO + 2nH 2 > C n H2n + nH 2 O nCO + (2n + 1) H 2 > C n H 2n+2 + nH 2 O The outcoming gaseous mixture is led to a condenser, where the liquid crude oil is obtained. The crude oil is fractionated to yield (i) gasoline and (ii) heavy oil. The heavy oil is used for cracking to get more gasoline. 4. Describe the manufacture of gasoline by Bergius method Bergius process (Direct method for the manufacture of gasoline) 1200 0 C 10
In this process the finely powdered coal is made into a paste with heavy oil and a catalyst powder (tin or nickel oleate) is mixed with it. The paste is pumped along with hydrogen gas into the converter, where the paste is heated to 400 450C under a pressure of 200 250 atm.
During this process hydrogen combines with coal to form saturated higher hydrocarbons, which undergo further decomposition at higher temperature to yield mixture of lower hydrocarbons. The mixture is led to a condenser, where the crude oil is obtained. The crude oil is then fractionated to yield (i) Gasoline (ii) Middle oil (iii) Heavy oil. The middle oil is further hydrogenated in vapour phase to yield more gasoline. The heavy oil is recycled for making paste with fresh coal dust. The yield of gasoline is about 60% of the coal used. 5. Describe the Otto- Hoffman method of coke manufacture and the recovery of various by products Otto-Hoffmans by product oven Inorder to (i) increase the thermal efficiency of the carbonisation process and, (ii) recover the valuable by products (like coal gas, ammonia, benzol oil, etc.) Otto- 11
Hoffman developed modern by product coke oven. The oven consists of a number of silica chambers. Each chamber is about 10 to 12 m long, 3 to 4 m height and 0.4 0.45 m wide. Each chamber is provided with a charging hole at the top, it is also provided with a gas off take valve and iron door at each end for discharging coke. Coal is introduced into the silica chamber and the chambers are closed. The chambers are heated to 1200C by burning the preheated air and the producer gas mixture in the interspaces between the chambers. The air and gas are preheated by sending them through 2nd and 3rd hot regenerators. Hot flue gases produced during carbonisation are allowed to pass through 1st and 4 th regenerators until the temperature has been raised to 1000C. While 1st and 4th regenerators are heated by hot flue gases, the 2nd and 3rd regenerators are used for heating the incoming air and gas mixture. Time taken for complete carbonisation is about 12-20 hours. The yield of coke is about 70%. The valuable by products like coal gas, tar, ammonia, H 2 S and benzol, etc. can be recovered from flue gas. Recovery of by - products i. Tar ii. Ammonia iii. Naphthalene iv. Benzene v. Hydrogen Sulphide (i)Tar The flue gases are first passed through a tower in which liquor ammonia is sprayed. Tar and dust get dissolved and collected in a tank below, which is heated by steam coils to recover back the ammonia sprayed. (ii) Ammonia 12
The gases are then passed through another tower in which water is sprayed. Here ammonia gets converted to NH 4 OH. (iii) Naphthalene The gases are again passed through a tower, in which cooled water is sprayed. Here naphthalene gets condensed. (iv) Benzene The gases are passed through another tower, where petroleum is sprayed. Here benzene gets condensed to liquid. (v) Hydrogen Sulphide The remaining gases are then passed through a purifier packed with moist Fe 2 O 3 . Here H 2 S is retained. The final gas left out is called coal gas which is used as a gaseous fuel. Advantages of Otto Hoffmans Process 1. Valuable by products like ammonia, coal gas, naphthalene etc., are recovered. 2. The carbonisation time is less. 3. Heating is done externally by producer gas. 6. Explain the fixed bed catalytic cracking for the manufacture of gasoline Fixed Bed Catalytic Cracking The heavy oil vapour is heated to 420 450C in a preheater. The hot vapours are then passed through a catalytic chamber, maintained at 425 450C and 1.5 kg/cm 2 pressure, where catalysts (artificial clay mixed with zirconium oxide), are kept in fixed beds. During this passage, through the catalytic chamber, about 40% of the heavy oil is converted into gasoline and about 2-4 % carbon is formed. 13
The carbon gets adsorbed on the catalyst bed. The cracked vapours are then passed through the fractionating column, where heavy oil gets condensed at the bottom. The vapours of gasoline are then sent through the cooler where gasoline gets condensed along with some gases. After 8-10 hours, the catalyst loses its activity due to the deposition of carbon. It is reactivated by burning off the deposited carbon. The gasoline containing some dissolved gases is then sent to a stabiliser, where the dissolved gases are removed and pure gasoline is recovered. 7. Explain the moving bed catalytic cracking for the manufacture of gasoline In this process, the solid catalyst is finely powdered, so that it behaves as a fluid, which can be circulated in oil vapour. 14
The heavy oil vapour is heated to 420 450C in a preheater and it is mixed with the catalyst powder. Then this mixture is forced into the reactor, which is maintained at a temperature of 500C and a pressure of 5 kg/cm 2 , where cracking takes place. Near the top of the reactor, there is a centrifugal separator (called cyclone), which allows only the cracked oil vapours to pass on to the fractionating column leaving behind the catalyst powder in the reactor itself. The catalyst powder gradually becomes heavier, due to coating of carbon and it settles down at the bottom of the reactor. Then it is forced into the regenerator maintained at 600C, where carbon is burnt and the regenerated catalyst is again recirculated along with the heavy oil vapour. From the reactor the cracked oil vapours are passed into the fractionating column, where heavy oil settles down and the vapours are then passed through the cooler where gasoline condenses along with some gases. The dissolved gases are separated from gasoline by passing it through a stabiliser. 8. How is water gas manufactured? State its composition and uses Manufacture of water gas The water gas producer consists of a tall steel vessel, lined inside with refractory bricks. It is provided with cup and cone feeder at the top and a side opening for water gas exit. At the bottom it is provided with two inlet pipes for passing air and steam.
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When steam and little air is passed alternatively over a red hot coke maintained at about 900 to 1000C in a reactor, water gas is produced. Various Reactions The reactions of water gas production involve the following two steps. Step - I In the first stage, steam is passed through the red hot coke, where CO & H 2 gases are produced. The reaction is endothermic. Hence, the temperature of the coke bed falls. C + H 2 O > CO + H 2 ; endothermic ; H = + ve Step - II In the second stage, in order to raise the temperature of the coke bed to 1000C, the steam supply is temporarily cut off and air is blown in. The reaction is exothermic. C + O 2 > CO 2 ; exothermic H = ve Thus the steam-run and air-blow are repeated alternatively to maintain proper temperature. Composition of water gas It is a mixture of CO and H 2 with small amount of N 2 . Constituents Percentage (%) CO 41 H 2 51 N 2 4 16
The average composition of water gas is as follows
9. How is producer gas manufactured? State its composition and uses Producer gas It is a mixture of CO & N 2 with small amount of H 2 . Its average composition is as follows. Constituents Percentage (%) CO 30 N 2 51-56 H 2 10-15 CO 2 + CH 4 rest
Its calorific value is about 1300 kcal/m 3
Manufacture The reactor used for the manufacture of produce gas is known as gas producer It consists of a tall steel vessel inside of which is lined with refractory bricks It is provided with cup and cone feeder at the top and a side opening for producer gas exit. At the bottom, it is provided with a inlet pipe for passing air and steam
CO 2 + CH 4 Rest 17
When a mixture of air and steam is passed over a red hot coke maintained at about 1100C in a reactor, the producer gas is produced. Various Reactions This is the lowest zone consists mainly of ash. The incoming air and steam mixture is preheated in this zone. (i) Ash Zone This is the lowest zone consists mainly of ash. The incoming air and steam mixture is preheated in this zone. (ii) Combustion (or) Oxidation Zone This is the zone next to ash zone. Here the coke is oxidised to CO and CO 2 . Both the reactions are exothermic. Hence, the temperature of the bed reaches around 1,100C. C + O 2 > CO ; exothermic C + O 2 > CO 2 ; exothermic (iii) Reduction Zone This is the middle zone. Here both CO2 and steam are reduced. C + CO 2 > 2CO ; endothermic C + H 2 O > CO + H 2 ; endothermic The above reactions are endothermic. Hence the temperature of the coke bed falls to 1000C. (iv) Distillation (or) Drying Zone This is the upper most layer of the coke bed. In this zone (400 800C) the incoming coke is heated by the outgoing gases. 18
10. How the flue gas analysis is carried out? Explain with diagram
Flue gas analysis by Orsat method The mixture of gases (like CO 2 , O 2 , CO, etc) coming out from the combustion chamber is called flue gases. The analysis of a flue gas would give an idea about the complete or incomplete combustion process. The analysis of flue gases is carried out by using orsats apparatus. Description of orsats apparatus It consists of a horizontal tube. At one end of this tube, U-tube containing fused CaCl 2 is connected through 3-way stop cock. The other end of this tube is connected with a graduated burette. The burette is surrounded by a water-jacket to keep the temperature of gas constant. The lower end of the burette is connected to a water reservoir by means of a rubber tube. The level of water in the burette can be raised or lowered by raising or lowering the reservoir. The horizontal tube is also connected with three different absorption bulbs I, II, and III for absorbing CO 2 , O 2 and CO. I-Bulb: It contains potassium hydroxide solution, and it absorbs only CO 2 . II-Bulb: It contains alkaline pyrogallol solution, and it absorbs CO 2 and O 2 . III-Bulb: It contains ammoniacal cuprous chloride solution and it absorbs CO 2 , O 2 and CO. Working 19
The 3-way stop-cock is opened to the atmosphere and the reservoir is raised, till the burette is completely filled with water and air is excluded from the burette. The 3-way stop-cock is now connected to the flue gas supply and the flue gas is sucked into the burette and the volume of flue gas is adjusted to 100 cc by raising and lowering the reservoir. Then the 3-way stop cock is closed.
(a) Absorption of CO 2
The stopper of the absorption bulb-I, containing KOH solution, is opened and all the gas is passed into the bulb-I by raising the level of water in the burette. The gas enters into the bulb-I, where CO 2 present in the flue gas is absorbed by KOH. The gas is again sent to the burette. This process is repeated several times to ensure complete absorption of CO 2 . The decrease in volume of the flue gas in the burette indicates the volume of CO 2 in 100 cc of the flue gas. (b) Absorption of O 2
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Stop-cock of bulb-I is closed and stop cock of bulb-II is opened. The gas is again sent into the absorption bulb-II, where O 2 present in the flue gas is absorbed by alkaline pyrogallol. The decrease in volume of the flue gas in the burette indicates the volume of O 2 . (c) Absorption of CO Now stop-cock of bulb-II is closed and stop-cock of bulb-III is opened. The remaining gas is sent into the absorption bulb-III, where CO present in the flue gas is absorbed by ammoniacal cuprous chloride. The decrease in volume of the flue gas in the burette indicates the volume of CO. The remaining gas in the burette after the absorption of CO 2 , O 2 & CO is taken as nitrogen. *******