EXECUTIVE SUMMARY

Hydrogen is a colourless, odourless and lightest gas known and present in most organic compounds. One of the widely used method of producing hydrogen is by passing steam through heated metal in the presence of a metal oxide catalyst. Hydrogen finds application in major industrial processes and the latest being its application as fuel in hydrogen powered automobiles. Hence there is need for more efficient, economical and effective method of production. PRODUCTION OF HYDROGEN FROM HEAVY OIL FEEDSTOCK THE PROCESS DESCRIPTION The major component of the feedstock is carbon, hydrogen and sulphur, which was mixed with preheated air (at 2100C) and steam at 600psig, 251.930C and passed into a combustor. Series of unit processes and operation were carried out such as sulphur removal, carbon removal etc (see process description). OPERATING CONDITIONS OF THE PROCESS. 1 2 Hydrogen purity Heavy fuel oil requirement 95 percent feed stock Viscosity of 900s containing carbon, hydrogen and sulphur Heat capacity of 42.9m/kg Specific gravity of 0.9435 Oxygen purity 95 percent at a temperature of 200c and a pressure of 4140kn/m2 Steam requirement pressure of 4140kn/m2 Cooling water requirement Temperature of 250c Electricity Voltage of 440v at 3-phase 50hz Crude gas 100% volume(dry basis) Saturated scrubbed gas Temperature of 350c

3 4. 5 6 7 8

MATERIAL OF CONSTRUCTION FOR AN ABSORBER: The materials for constructing the absorber are as follows: Stainless Steels Alloy Steels Other Plastic Materials Rubber Lined Steel Plastic Coatings
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There are various types of absorbers depending on whether the components to be absorbed are in a solid, liquid, or gaseous state. They are: Open spray towers Packed towers Tray towers The safety challenge is of two-folds: 1. Address the known risks (e.g. H2 leak) in a way that is compatible with the operation. The conventional methods used by industry (large clearance distances, personnel protective equipment) are not easily applicable here; 2. Discover and address all the new risk factors brought in by the new elements above and their combination. Hydrogen gas forms explosive mixture with air if it is 4-74% concentrated and with chlorine if it is 5-95% concentrated. The mixture spontaneously explode with spark, heat or sunlight. Pure hydrogenoxygen flame emits ultraviolet light and are nearly invisible to the naked eyes. Hydrogen can react spontaneously and violently at room temperature with chlorine and fluorine to form the corresponding hydrogen halides, hydrogen chlorides and hydrogen fluoride which are also potentially dangerous acids. ECONOMY Hydrogen can be used as potential fuel for motor power (including cars and boats), the energy needs of building and portable

electronics.Hydrogen is an energy carrier (like electricity) not a primary energy source (like coal).

INTRODUCTION
Following the new regulation in the last years, defining more stringent limits for the emissions to the atmosphere, the necessity to find an alternative use for the fuel oil has created a new challenge for the refineries. At the same time the need to improve power production has pushed energy companies, to enter the electricity market. In this frame we have decided to design a new combined-cycle power plant to produce 20 million standard cubic feet per day of Hydrogen of at least 95 per cent purity in which the process employed is the partial oxidation of oil feedstock. Hydrogen is a naturally occurring gas that is amazingly light it is in fact, the lightest gas ever found which has no color, no smell and no taste. Hydrogen is one of the most reactive substances in the world which is also very flammable. Pure hydrogen gas is very hard to come by, this means that hydrogen may need to be produced artificially, from either fossil fuels or water. The splitting of hydrogen compounds uses a lot of energy, Currently most hydrogen is made by passing steam through natural gas, creating a compound of carbon monoxide and hydrogen. The compound is purified by changing the carbon monoxide to carbon dioxide and then the carbon dioxide is dissolved in water. Hydrogen is left behind after this process.

The partial oxidation of heavy fuel oil feedstock is as an integral building block for hydrogen production in the refining scheme whereby a feed consisting of Carbon, Hydrogen and Sulphur are fed to a reactor with Oxygen and Steam to give products which undergo three major stages to obtain hydrogen in a pure form of at least 95% purity. The three major stages are: CO conversion H2S removal CO2 removal 3

Our objective is therefore to accomplish these tasks using a maximum of proven technology to produce a marketable product slate. Apart from the partial oxidation method, oxygen can also be prepared in other various processes such as, the haber process in fertilizers industries (from ammonia), steam reforming (burning natural gas), direct water splitting with high energy input, electrolysis and thermolysis under high

temperature(this is the most expensive processes), coal carbonization, reduction of metal oxide, In spite of all this various processes of hydrogen production, the partial oxidation method is widely used in the industries and refineries because it has some advantages over other process which are: (1) It is the cheapest method (2) It minimizes the rate of environmental pollution such as; reducing sulphur, carbon(iv)oxide and nitrogen(iv)oxide emissions. (3) Low energy input USES OF HYDROGEN. Production of electricity in power stations Production of paints Fertilizer production Petrochemical industries (hydro-treating processes). Steel production. Even with all these processes more research are still on for a more efficient, economical and environmental friendly methods for the

production of hydrogen.

LITERATURE REVIEW
Hydrogen is a major gas which is widely used in almost every sector of production in the industry for producing gases, power, and several other components for mans utilization. As earlier stated in the introduction, there are various method of hydrogen production, but our case study which is the partial oxidation of heavy fuel oil is one of the most wide spread method of hydrogen production. It involves the conversion of steam, oxygen and hydrocarbons to hydrogen and carbon oxides with or without catalyst. The catalytic process which was used in this plant design included two stages of catalytic conversion at a temperature of 370C and pressure of 4140KN/m2. Generally, it is first necessary to prepare the fuel for feeding to the reactor in the presence of preheated oxygen and steam whereby reaction takes place and the product (gas) is treated to remove particulates and other components that may be detrimental to the downstream processes. From a process perspective, partial oxidation of gases and liquids is very similar to the gasification of solids. The term gasification is used to refer to all the applications of the various unit operations carried out in this design process. A wide variety of feed stocks can be considered for gasification, ranging from solids to liquids to gaseous streams. Although when the feed is a gas or liquid, the operation is frequently referred to as partial oxidation (POX). The major requirement for a suitable feedstock is that it contains a significant content of carbon and hydrogen. Oxygen at 99.5%v purity will be supplied from an air separation unit and will be preheated prior to being introduced into the reactor (combustor). The heat required to heat the feed streams and the extent of complete combustion which occurs is a function of the amount of oxygen co-fed to the combustor. Gasification temperature is controlled by the addition of water or steam and for slurry feed stocks, the slurry water accomplishes this control. For other feed stocks, such as heavy oils as used in this 5

process, steam is injected with the feedstock to control temperature. This steam injection may also be used to adjust the composition of the product from the combustor (mixture of crude gas and carbon particles. The following reaction take place in the oil mixture; CnHm + n/2CO2 CnHm + H2O CO + H2O

nCO + m/2H2 nCO + (n+m)/2H2

CO2 + H2

The cleaned gas is then sent to the column where the hydrogen content is increased and fed to a purification section where it is upgraded to meet the end use requirements of hydrogen of at least 95 per cent purity. The optimal design of a hydrogen production and purification system is based on the following set of criteria: hydrogen demand required hydrogen delivery purity and pressure hydrogen recovery efficiency total plant integration opportunities system reliability, availability and maintenance requirements capital and operating costs The choice of method employed for hydrogen prodution will depend on feedstock availability, the physical characteristics of the feed, the temperature and pressure needed to optimize the desired product yields. If ultra pure hydrogen is required i.e. hydrogen of at least 95 percent purity, either pressure swing adsorption or cryogenic separation will probably have to be employed but if hydrogen purity is to be below 95 percent, membrane separation can be used to purify the gas. In the selection of the process units in the cleanup section which comprises of the quencher, scrubber, the saturator and desaturator, the various absorbers, and measures applied for the final hydrogen

purification, is dependent on the quality of the raw gas from the reaction and the ultimate end-use of the product hydrogen. In this case, filters were used for particulate removal of gases such as carbon from the 6

quencher. Also, the sulphides and ammonia can be removed with the use of a variety of commercial processes which include both regenerable and non-regenerable solid adsorption and liquid absorption processes. The carbon dioxide in the gas may be removed or absorbed by utilizing one of the commercial liquid absorption processes that employ either a physical solvent or a regenerated chemical solvent such as an amine or hot potassium carbonate. From the various methods of hydrogen production, steam reforming is the method that has a close relationship with the partial oxidation of heavy fuel oil as it involves the burning of natural gas. Steam reforming or partial oxidation is used to maximize hydrogen content of the gas. Steam reforming has the advantage of being a well-established process. Its disadvantage is it requires steam and a separate heating source to provide the heat of reaction. In contrast, partial oxidation is an emerging technology and the heat of reaction is generated in the reactor by combustion of some of the feed.

DESCRIPTION OF THE PROCESS

Heavy fuel oil feedstock is delivered into the suction of metering-type ram pumps which feed it via-a steam preheater into the combustor of a refractory-lined flame reactor. The feedstock must be healed to 200C in the preheater to ensure efficient atomization in the combustor. A mixture of oxygen and steam is also fed to the combustor, the oxygen being preheated in a separate steam preheater to 210C before being mixed with the reactant steam. The crude gas, which will contain some carbon particles, leaves the reactor at approximately 1300C and passes immediately into a special waste-heat boiler where steam at 600 psig (4140 kN/m2 gauge) is generated. The crude gas leaves the waste heat boiler at 250C and is further cooled to 50C by direct quenching with water, , which also serves to remove the carbon as a suspension. The analysis of the quenched crude gas is as follows: H2 47.6 percent vol (dry basis)

CO2 8.3 percent vol (dry basis) CO CH4 42.1 percent vol (dry basis) 0.I percent vol (dry basis)

H2S 0.5 percent vol (dry basis) N2 1.40 percent vol (dry basis) 100.0 per cent vol (dry basis) For the primary flame reaction steam and oxygen arc fed to the reactor at the following rales: Steam 0.75 kg/kg of heavy fuel oil feedstock Oxygen 1.16 kg/kg of heavy fuel oil feedstock. The carbon produced in the flame reaction, and which is subsequently removed as carbon suspension in water, amounts to 1.5 per cent by weight of the fuel oil feedstock charge. Some I-I2S present in the crude gas is removed by contact with the quench water. The quenched gas passes to an H2S removal stage where it may be assumed that H2S is selectively scrubbed down to 15 parts per million with 8

substantially nil removal of CO2. Solution regeneration in this process is undertaken using the waste low-pressure steam from another process. The scrubbed gas, at 35C and saturated, has then to undergo CO conversion, final H2S removal, and CO2 removal to allow it to meet the product specification. CO conversion is carried out over chromium-promoted iron oxide catalyst employing two stages of catalytic conversion; the plant also incorporates a saturator and desaturator operating with a hot water circuit. Incoming gas is introduced into the saturator (a packed column) where it is contacted with hot water pumped from the base of the desaturator; this process serves to preheat the gas and to introduce into it some of the water vapour required as reactant. The gas then passes to two heat exchangers in series. In the first, the unconverted gas is heated, against the converted gas from the second stage of catalytic conversion; in the second heat exchanger the unconverted gas is further healed against the converted gas from the first stage of catalytic conversion. The remaining water required as reactant is then introduced into the unconverted gas as steam at 000 psig (4140 kN/m2 gauge) saturated and the gas/steam mixture passes to the catalyst vessel at a temperature of 3700C. Thecatalyst vessel is a single shell with a dividing plate separating the two catalyst beds which constitute the two stages of conversion. The converted gas from each stage passes to the heat exchangers previously described and thence to the desaturator, which is a further packed column. In this column the converted gas is contacted

countercurrent with hot water pumped from the saturator base; the temperature of the gas is reduced and the deposited water is absorbed in the hot-water circuit. An air-cooled heat exchanger then reduces the .temperature of the converted gas to 40C for final H2S removal. Final H2S removal takes place in four vertical vessels each approximately 60 feet (18.3 m) in height and 8 feet (2.4 m) in diameter and equipped with five 9

trays of iron oxide absorbent. Each vessel is provided with a locking lid of the autoclave type. The total pressure drop across these vessels is 5 psi (35 kN/m2). Gas leaving this .section of the plant contains less than 1ppm of H2S and passes to the CO2 removal stage at a temperature of 35C. CO2 removal is accomplished employing high-pressure potassium carbonate wash with solution regeneration.

THE HYSIS PROCESS FLOW DIAGRAM:

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MATERIAL BALANCE BASIS: HYDROGEN

PRODUCT: Hydrogen SPECIFICATION: 6.424m3/sec CONDITION: Temperature=308k, pressure=172.42*103N/m2 Hydrogen is quench crude gas C0NDITION: Temperature=323k, pressure=206.9*103N/m3 P1*V1/T1=P2*V2/T2 P1=206.9*103N/m2 T1=323K P2=172.42*103N/m2 T2=308K V2=6.424m3/sec V1= V1=P2*V2*T1/(P1*T2) =172.42*6.424*323/(206.9*308) V1=5.614m3/sec COMPONENT OF QUENCH CRUDE GAS H2=47.6%v CO=42.1%v CO2=8.3%v CH4-0.1%v H2S-0.5%v N2-1.4%v Let the total volume of quench gas be P, where volume of Hydrogen in quench crude gas is 5.614m3/sec
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47.6*P/100=5.614 P=11.794m3/sec Component of quench crude gas in volume H2=5.614m3/sec CO=42.1*11.794/100 =0.978m3/sec Co2 =(8.3/100)*11.794 = 0.978m3/sec CH4=(0.1/100)*11.794 =0.0118m3/sec H2S=(0.5/100)*11.794 =0.0589m3/sec N=(1.4/100)*11.794 =0.165m3/sec NB: N2 feed into the reactor at 483k, pressure-206.9*103N/m2 Recall from Charles law; V1/T1=V2/T2 V1=V2*T1/T2 =483*0.165/323 =0.247m3/sec NB; moles of N2 entering the reactor=moles of N2 leaving the reactor From ideal gas law, PV=nRT n=PV/RT =(206.9*103*0.247)/8.314*483 =12.73mol/sec Converting to mass; mass=moles*molar mass 12.73*(14*2)
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=0.356Kg/sec Since air is 95% of oxygen and 5% nitrogen Air supplied= (5/100)*Air=0.356 Air= (0.3559*100)/5 Air=7.127kg/sec Oxygen supplied=(95/100)*7.127 =6.7704kg 1.16kg of oxygen----------------------------------------------------1kg of heavy fuel oil 6.7704kg----------------------------------------------------------------x Therefore; x=1kg of heavy fuel oil*6.7704kg of oxygen/1.6kg of oxygen =5.84kg of heavy fuel oil at 483k Therefore moles of heavy fuel oil at 483k and 206.9*103N/m Also, mass of heavy fuel oil supplied=5.84kg of heavy fuel oil Carbon=(85/100)*5.84 =4.964kg/12kg/kmoles =413.667moles Hydrogen=(11/100)*5.84 =0.6424/kg/1kg/kmole =642.4mole Sulphur=(4/100)*5.84 =0.2336kg/32kg/kmole =7.3moles Amount of carbon suspension removed is (1.5/100)*5.84 =0.0876kg of carbon suspension H2S removed of saturated scrubber gas H2S at 323k=0.0589m3/sec At 308k; from Charles law, V1/T1=V2/T2
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Therefore, 0.0589/323=v2/308 V2==0.05616m3/sec at 308k If 15ppm of H2S removed =0.0562-(15*10-6)*0.056 =0.0561m3/sec removed Amount of H2S left=8.424*10-7m3/sec Conversion of CO to CO2 Therefore CO+1/2O2-------CO2 CO : CO2 1 : 4.965M3/S 1

: 4.965M3/S

Total CO2 formed=4.95+0.978=5.943m3/sec Amount of H2 Removed finally at 308k =8.424*10-7 m3/secProduct out of the process H2 CH4 H2O Nv 1 x 10-6 m3/secs at 350C 308k 6.424 m3/secs

V1T2 = V2T1 For T1 =323k = SS V1 =0.165 1 m3/s 0.1651 x 307 = V2 x 323 N2 = 0.1574 m3/s CH4 at 350C = 308k For T1 = 323k, V1 = 0.0118 m3/s V2 = (0.0118 x 308)/323 CH4 = 0.0113 m3/s

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ENERGY BALANCE AROUND THE REACTOR: Assumptions: Flow rate of air and steam is constant Cp of air (T-T1) = Cp of steam (252.31 T) 25.67 (T-210) = 2799.57 (252.31 T) T = 251.93oC Energy balance within and out of the reactor: From the reaction; 2C + O2 = 2CO C + O2=CO2 H2 + S= H2S Calculating the various enthalpies from the relations: a + bT + Ct2= cp Cp for carbon = specific heat capacity From carbon Cp= 11.18 + 1.095*10-2(473)-4.89*10-5(473)-2 =16.359 2 Cp of carbon =2*16.359 =32.7187 Cp of O2 =29.10 +1.158*10-2(200) 0.6076*10-5*(200)-2 =31.416 Cp of sulphur = 2.68 Cp of H = 28.84 + 0.00765*10-2(200) + 0.3288*10-5(200)-2 =28.85 Cp of N2=29.44 NB; heat loss= heat gained around reactor Heat losses from the fuel gases, air, and steam are CARBON m Cp T =32.718*(1300-200)*0.6424
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=23119.7475j/gmole/k HYDROGEN 4.964*(1300-200)*28.85 =157532.54j/gmolek SULPHUR 0.2336*(1300-200)*2.68 =688.6528j/gmole.k AIR Cp of air=28.94+0.4147(210) +0.319*10-2(210)-2 =116.027 M Cp air* T =7.127*116.027(1300-210) =901347.63j/gmolek STEAM Cp =4140 M=7.127(same with air) H = mcpT =7.127*4140(1300-251.93) =30924122.84j/gmolek Therefore Total energy inlet= total energy outlet n=ii=1 Hn=2311908475+157532054+688.6528+901347.63+30924122.84 =32006811.51j/gmolek =32006811j/gmole.k

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CHEMICAL ENGINEERING DESIGN FOR THE PROCESS

There are six (6) stages which describes this partial oxidation process in details, they are; (1) REACTION OF FEED: The heavy fuel oil fed to the combustor reacts with the input preheated oxygen and steam in which the product consisting of crude gas and carbon particles leaves at approximately 1300C to a waste heat boiler where steam is generated at 4140KN/m2. (2) REMOVAL OF CARBON: The product from the waste boiler enters the quencher which removes the carbon particles as a suspension at 50C. Some H2S in the crude was also removed at this stage while some more were selectively scrubbed down when the quenched gas was passed into the scrubber. (3) CONVERSION OF CARBONMONOXIDE: chromium-promoted ironoxide This was carried out over where the catalytic

catalyst

conversion took place in two stages involving the saturator, two heat exchangers in series and a desaturator. The converted gas was cooled at 40C and transferred to four (4) absorbers. (4) REMOVAL OF HYDROGEN SULPHIDE: The absorbers absorbs the

H2S in the presence of iron oxide absorbent whereby the gas leaving this section contained H2S less than 1ppm at a total pressure drop of 35KN/m2 across the four vessels. (5) REMOVAL OF CARBON(IV)OXIDE: presence of At a temperature of 35C, in the

a high-pressure potassium carbonate wash with

solution regeneration, the CO2 is absorbed in the absorber to produce hydrogen with impurities. (6) PURIFICATION OF HYDROGEN: The gas produced after CO2

removal, is sent to this section where the specification is made to meet up the end requirement of hydrogen at 95 percent purity.

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OPERATING CONDITIONS OF THE PROCESS.

1 2 Hydrogen purity Heavy fuel oil feed 95 percent stock Viscosity of 900s containing

requirement

carbon, hydrogen and sulphur Heat capacity of 42.9m/kg Specific gravity of 0.9435

Oxygen purity

95 percent at a temperature of 200c and a pressure of

4140kn/m2 4. 5 6 7 8 Steam requirement Cooling water requirement Electricity Crude gas Saturated scrubbed gas pressure of 4140kn/m2 Temperature of 250c Voltage of 440v at 3-phase 50hz 100% volume(dry basis) Temperature of 350c

MATERIAL OF CONSTRUCTION FOR AN ABSORBER:

The materials for constructing the absorber are as follows: Stainless Steels Alloy Steels FRP Other Plastic Materials Rubber Lined Steel Plastic Coatings There are various types of absorbers depending on whether the

components to be absorbed are in a solid, liquid, or gaseous state. They are: Open spray towers Packed towers Tray towers

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SAFETY MEASURES
ENVIRONMENTAL IMPACT
Hydrogen is widely used today as a chemical product in various industries (petrochemical, food, electronics, metallurgical processing etc.). So far, the only significant energy application has been space programs. Hydrogen is however emerging as a major component for a future sustainable energy economy where hydrogen and electricity are foreseen to be complimentary sustainable energy carriers1 with hydrogen

especially valid for movable or portable applications. Hydrogen offers a unique method of reducing the fossil fuel dependency while increasing the usage of renewable energy sources. The main driving forces to introduce hydrogen as an energy carrier are based on the limited fossil fuel resources in general, and the implicit political dependencies creating a widespread and high level political need to secure and diversify national energy supplies2. Environmental concerns on urban pollution and the greenhouse effect are also important drivers concerns over environmental impacts of continued fossil fuel use are leading to development of decarbonisation technologies. In the short term, it is believed that such technologies will be a source for low-cost hydrogen production. Currently about 90 percent of the worlds hydrogen production is based on fossil fuels and mainly natural gas4. In the long term, the production needs to be based on the renewable energy sources in order to reduce the pollution problem in a sustainable way. In the mean time hydrogen production might be based on fossil fuels (natural gas reforming, coal gasification) with CO2 sequestration and H2 production at nuclear installations. The safety challenges result not only from the implementation of hydrogen technology for use directly by the public in a non-industrial context and for 19

a completely new application. It lies also in the demanding performance and cost targets imposed by the applications leading to: the excursion to new domains of service conditions the introduction of new physical processes the use of new materials

The safety challenge is of two-folds: 1. Address the known risks (e.g. H2 leak) in a way that is compatible with the operation. The conventional methods used by industry (large

clearance distances, personnel protecttive equipment) are not easily applicable here; 2. Discover and address all the new risk factors brought in by the new elements above and their combination. Hydrogen gas forms explosive mixture with air if it is 4-74% concentrated and with chlorine if it is 5-95% concentrated. The mixture spontaneously explode with spark, heat or sunlight. Pure hydrogen-oxygen flame emits ultraviolet light and are nearly invisible to the naked eyes. Hydrogen can react spontaneously and violently at room temperature with chlorine and fluorine to form the corresponding hydrogen halides, hydrogen chlorides and hydrogen fluoride which are also potentially dangerous acids. ECONOMY Hydrogen can be used as potential fuel for motor power (including cars and boats), the energy needs of building and portable electronics. Hydrogen is an energy carrier (like electricity) not a primary energy source (like coal). The utility of a hydrogen economy depends on issues of energy sourcing, including fossil fuel use, climate change and sustainable energy generation.

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CONCLUSION
From the process description, energy, material balance and process design, the method of producing hydrogen from heavy oil feedstock is an efficient and effective one. From the energy balance carried out around the reactor mixer system, a total energy of 32006.811kJ/gmol0c will be needed to produce 20 x 106 standard cubic feet of hydrogen per day of 95% purity.

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REFERENCES
A. Eucken, PhysikZ. 14, 324 (1913). A. Eucken, PhysikZ. 14, 324 (1913). C. Higman & G. Grnfelder, "Clean Power Generation from Heavy Residues", Inst. Mech. Eng., Nov 1990. C. R. Wilke, J . Chem. Phys. 17, 550 (1949). C. R. Wilke, J . Chem. Phys. 17, 550 (1949). E. J. Owens and G. Thodos, AIChE J. 3, 454 (1957). E. J. Owens and G. Thodos, AIChE J. 3, 454 (1957). E. Stldt, "Concepts for Zero Residue Refineries", Interpec China '91, Beijing, Sept 1991. E. Stldt, "Concepts for Zero Residue Refineries", Interpec China '91, Beijing, Sept. 1991. F. Fesharaki & D. Isaak, "Crisis means changes for oil market, OPEC", Oil & Gas Journal, Nov 1990. F. Fesharaki & D. Isaak, "Crisis means changes for oil market, OPEC", Oil & Gas Journal, Nov 1990. G. Heinrich, M. Valais, M. Passot and B. Chapotel, "Mutations of World Refining: Challenges and Answers", Ptrol et Techniques, April/May 1992. G. Heinrich, M. Valais, M. Passot and B. Chapotel, "Mutations of World Refining: Challenges and Answers", Ptrol et Techniques, April/May 1992. G. Wiedemann and R. Franz, Annu. Phys. Chem. 89, 530 (1853). G. Wiedemann and R. Franz, Annu. Phys. Chem. 89, 530 (1853).

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