ASSIGNMENT

(Technical Service Department)

Diesel Max Process Unit

Table of Contents

Q.1 Feed Surge Drum.............................................................................................. 2 Q.2 Temperature Run Away In Diesel-Max Reactor ................................................. 2 Q.3 Wash Water Specs ........................................................................................... 2 Q.4 Design Parameters of Recycle Gas Compressor (284 C-1) .................................. 3 Q.5 Crude Oil Assay ............................................................................................... 3 Q.6 Lubricity ........................................................................................................... 7 Q.7 WABT & LHSV Calculations .............................................................................. 10 Q.8 Temperature Monitoring Philosophy in Reactors ............................................. 14 Q.9 Flooding in Fire Heaters ................................................................................... 17

Q.10 Refractory and its types ................................................................................ 18 Q.11 Heat Distribution in Heaters .......................................................................... 22 Q.12 Difference between TBP Curve and ASTM D-86 ......................................... 23

Q#1: The feed surge drum is horizontal at DHDS whereas it is vertical at Diesel max. Give reason? Answer: The reason of installation difference of feed surge drum at these two units is the different head requirement. The head required at DHDS is 53kg/cm2 so feed surge drum is installed horizontally; whereas head required at Diesel max is greater i.e. 110kg/cm2 so here the feed surge drum is installed vertically. Q#2: How to control temperature run away in Diesel Max Reactor? Why quenching is done in Diesel Max Reactor? Answer: Diesel Max reactor consists of four fixed beds. Different type of reactions occurred in these reactors, but almost all of them are exothermic in nature i.e. heat will be produced by the reactions. So temperature will be increased after each bed and there will be a chance of temperature run away in the reactor. Quenching is done to reduce the temperature after each bed of catalyst. It is done with hydrogen and it maintains the overall temperature in the bed. Temperature run away in the reactor is extremely dangerous and it can totally damage the reactor and catalyst. Extra care should be taken to avoid temperature run away in reactor. Following are the precautionary steps, in order to avoid temperature run away in reactor: 1. Dont exceed temperature difference in each bed above 42 oC. Temperature of each bed should be closely monitored. 2. When making any change in feed rate, increase feed rate first then increase catalyst temperature. Conversely when decreasing feed rate, decrease the temperature of bed first then decrease the feed rate. 3. Make catalyst temperature increase gradually and smoothly. The temperature can be safely increased depending on catalyst age and severity of operation. Fresh catalyst is more sensitive to temperature. 4. If any upsets in flow are observed, immediately reduce reactor inlet temperature. Loss of any of streams flowing through reactors will result in less heat removal capability and could lead to temperature run away. 5. All operating personnel should be thoroughly familiar with emergency procedures to protect catalyst and equipment in case of any temperature run away. Q#3: How to check whether wash water injection is sufficient in Diesel Max? Also write wash water specs. 2

Answer: Wash water is injected to dissolve ammonium salts and to avoid precipitation of these salts on temperature reduction. Wash water injection rate should be monitored closely to avoid any fouling of equipment. Both physical and chemical analysis of wash water is done to make sure that water injection is sufficient. Physically colour of water is observed by operators and with experience they decide whether water injection is sufficient or not. Also water samples are taken at regular intervals. In chemical analysis pH, chloride contents, iron contents and salts etc. in water samples are observed and on the basis of these results, water injection rate is decided. Wash water specs Total dissolve solids = 25 wt-ppm max Chloride = 5 wt-ppm max Free oxygen gas = 50 wt-ppb max NH3 = 100 wt-ppm max H2S = 100 wt-ppm max pH = 7-9

Q#4: Write design parameters of recycle gas compressor (284-C1) of Diesel Max. Answer: Following are the general properties of the recycle gas compressor of Diesel Max unit: Inlet Pressure (Operating pressure = 69.13 Kg/cm2, rated pressure = 70 kg/cm2) Inlet Temperature (Operating temperature = 54 oC, rated temperature = 60 oC) Discharge Pressure (Operating pressure = 96.36 Kg/cm2, rated pressure = 99.25 kg/cm2) Discharge Temperature (Operating temperature = 92 oC, rated temperature = 96 oC) Flow rate (operating flow = 23967 kg/hr , rated flow = 26364 kg/hr) Rated Power = 2109 kw Compressibility = 1.3535

Q#5: Explain crude oil assay Introduction A crude oil assay is essentially the chemical evaluation of crude oil feedstocks by petroleum testing laboratories. Each crude oil type has unique molecular, chemical characteristics. No crude oil type is identical and there are crucial differences in crude oil quality. The results of crude oil assay testing provide extensive detailed hydrocarbon analysis data for refiners, oil traders and producers. Assay data help refineries determine if a crude oil feedstock is compatible for a particular petroleum refinery or if the crude oil could cause yield, quality, production, environmental and other problems. The assay can be an inspection assay or comprehensive assay. Testing can include crude oil characterization of whole crude oils and the various boiling range fractions produced from physical or simulated distillation by various procedures. Information obtained from the petroleum assay is used for

detailed refinery engineering and client marketing purposes. Feedstock assay data are an important tool in the refining process. Crude Oil Components Petroleum includes only crude oil, but in common usage it includes all liquid, gaseous, and solid hydrocarbons. Under surface pressure and temperature conditions, lighter hydrocarbons methane, ethane, propane and butane occur as gases, while pentane and heavier ones are in the form of liquids or solids. However, in an underground oil reservoir the proportions of gas, liquid, and solid depend on subsurface conditions and on the phase diagram of the petroleum mixture. The proportion of light hydrocarbons in the petroleum mixture varies greatly among different oil fields, ranging from as much as 97 percent by weight in the lighter oils to as little as 50 percent in the heavier oils and bitumens. The hydrocarbons in crude oil are mostly alkanes, cycloalkanes and various aromatic hydrocarbons while the other organic compounds contain nitrogen, oxygen and sulfur, and trace amounts of metals such as iron, nickel, copper and vanadium. The petroleum industry generally classifies crude oil by the geographic location it is produced, its API gravity, and its sulfur content. Crude oil may be considered light if it has low density or heavy if it has high density; and it may be referred to as sweet if it contains relatively little sulfur or sour if it contains substantial amounts of sulfur.

Crude assay evaluations Atmospheric and vacuum distillations producing distillate fractions and residual bottoms similar to the actual refining process. Crude oil general properties analysis produces data including sulfur content, nitrogen content, viscosity measurements, cold property measurements and metals content. Detailed hydrocarbon analysis of crude oil off-gas is also run. Crude oil assays vary in depth and complexity, dependent upon crude oil type and customer requirements. Example of Crude Assay Arab Light Crude Oil ORIGIN Saudi Arabia CRUDE REFERENCE SAMPLE DATE Whole Crude Inspection 4

Arab Light ARBL91A 1991

Density @ 15 C, g/cc Sulphur, wt % Nitrogen, ppm Pour Point, C Viscosity @ 40 C (104 F), cSt Viscosity @ 50 C (122 F), cSt

0.8576 1.77 887 -53.9 8.04 6.83

TBP YIELDS, WGT % Light Gasoline (IBP-70 C) Light Naphtha (70-140 C) Heavy Naphtha (140-200 C) Kerosene (200-260 C) Atmospheric Gas Oil (260-350 C) Light Vacuum Gas Oil (350-430 C) Heavy Vacuum Gas Oil (430-570 C) Vacuum Residue (570 C+)

4.906 9.045 10.640 10.851 15.804 12.956 18.441 17.356

LIGHT GASOLINE (IBP-70 C) Yield, wgt % Density @ 15 C, g/cc MercaptanSulphur, ppm Research Octane Number

4.906 0.6325 63.2 74.6

LIGHT NAPHTHA (70-140 C) Yield, wgt % Density @ 15 C, g/cc MercaptanSulphur, ppm Naphthenes, wt % Aromatics, wt % Research Octane Number

9.045 0.7235 152 17.87 12.11 45.4

HEAVY NAPHTHA (140-200 C) Yield, wgt % Density @ 15 C, g/cc Sulphur, wt % MercaptanSulphur, ppm Naphthenes, wt % Aromatics, wt %

10.640 0.7733 0.0695 55.8 19.19 21.39 5

Smoke Point, mm (ASTM)

25.6

KEROSENE (200-260 C) Yield, wgt % Density @ 15 C, g/cc Sulphur, wt % MercaptanSulphur, ppm Naphthenes, wt % Aromatics, wt % Freeze Point, C Smoke Point, mm (ASTM) Viscosity @ 50 C (122 F), cSt

10.851 0.8100 0.425 23.0 21.48 24.74 -32.3 21.5 1.4

ATM. GAS OIL (260-350 C) Yield, wgt % Density @ 15 C, g/cc Sulphur, wt % Nitrogen, ppm Pour Point, C Viscosity @ 50 C (122 F), cSt Cetane Index

15.804 0.8510 1.32 97.0 -2.3 3.51 57.3

ATMOSPHERIC RESIDUE (350 C+) Yield, wgt % Density @ 15 C, g/cc Sulphur, wt % Nitrogen, ppm Conradson Carbon Residue, wt% Asphaltenes, wt % (C5 Insolubles) Nickel, ppm Vanadium, ppm Pour Point, C Viscosity @ 50 C (122 F), cSt Viscosity @ 100 C (212 F), cSt

48.753 0.9551 3.09 1780 6.08 1.92 6.82 27.3 3.2 188 25.8

LIGHT VACUUM GAS OIL (350-430 C) Yield, wgt % Density @ 15 C, g/cc

12.956 0.8938 6

Sulphur, wt % Nitrogen, ppm Pour Point, C Aniline Point, C Viscosity @ 50 C (122 F), cSt Viscosity @ 100 C (212 F), cSt

2.10 399 20.1 78.0 10.4 3.58

HEAVY VACUUM GAS OIL (430-570 C) Yield, wgt % Density @ 15 C, g/cc Sulphur, wt % Nitrogen, ppm Pour Point, C Aniline Point, C Viscosity @ 50 C (122 F), cSt Viscosity @ 100 C (212 F), cSt

18.441 0.9420 2.76 1210 33.6 84.2 59.3 11.5

VACUUM RESIDUE (570 C+) Yield, wgt % Density @ 15 C, g/cc Sulphur, wt % Nitrogen, ppm Conradson Carbon Residue, wt% Asphaltenes, wt % (C5 Insolubles) Nickel, ppm Vanadium, ppm Pour Point, C Viscosity @ 50 C (122 F), cSt Viscosity @ 100 C (212 F), cSt Viscosity @ 135 C (275 F), cSt 212

17.356 1.0227 4.19 3430 16.8 5.35 19.1 76.6 47.0 128000 1400

Q#6: what is the lubricity property of a fuel? Define lubricity of diesel and How is measured? Also describe the way of improving lubricity and chemicals used for this purpose? Introduction The term lubricity is often defined as the ability of a lubricantin this case diesel fuelto minimize friction between and damage to surfaces in relative motion under load. Generally the tests used to evaluate diesel fuel lubricity try to create conditions of boundary lubrication. More specifically, test 7

results that quantify a fuels lubricity are a measure of the fuels ability to minimize friction between and/or damage to surfaces in relative motion under boundary lubrication conditions. For this reason lubricity is also termed a substance's anti-wear property. Types of Lubricity Test methods Different types of methods have been developed to measure fuel lubricity: Vehicle tests:- In a vehicle test , the vehicle is operated on the fuel for a specified length of time or a specified distance. The fuel system components can then be disassembled and examined for wear. This test has the advantage of being the most representative of real-world conditions and can measure all possible wear related failures not just those associated with boundary lubrication. Tests of this nature are however very expensive and time consuming and do not lend themselves to testing a large number of fuel combinations. Pump rig tests:-An alternative to the vehicle test is a pump rig test (ASTM D6898). In a pump rig test, a fuel injection pump is mounted on a test stand and is driven by an electric motor. Fuel is circulated through the pump for a specified period of time. The pump and any other equipment attached to it can then be disassembled and examined for wear and other deleterious effects. This test has the advantage of being less costly than a full vehicle test while maintaining the ability to test for many wear related failures beyond those associated with boundary lubrication. It is still time consuming and expensive to operate. One test can require as much as 500-1000 hours of test time. Pump rig tests are often necessary to evaluate the effectiveness of much simpler bench tests. Bench tests:- A number of bench tests that try to recreate boundary lubrication conditions similar to those found in fuel injection equipment have been developed to allow rapid and relatively inexpensive measurements of fuel lubricity:
o

The Ball-on-Cylinder Lubricity Evaluator (BOCLE) was developed for aviation jet fuels. It continues to be used for this application. It is particularly useful for measuring the effects of fuels and additives on oxidative wearan important wear mechanism in aviation fuel systems. The Scuffing Load Ball-on-Cylinder Lubricity Evaluator (SLBOCLE) was developed in the mid 1990s in response to diesel fuel system failures resulting from the introduction of low sulfur diesel fuels. It is similar to the BOCLE test but with modifications to make it less sensitive to oxidative wear and more sensitive to adhesive scuffing. The High Frequency Reciprocating Rig (HFRR) was also developed in the 1990s to make it useful for evaluating diesel fuel lubricity. It can produce a wide range of wear mechanisms depending on the fuel being tested. The Ball on Three Disks (BOTD) method is fairly recent and is still in the development phase. It is a compact and more economical version of the Ball on Three Seats apparatus.

Lubricity Benefits Provided by Biodiesel The addition of biodiesel, even in very small quantities, has been shown to provide increases in fuel lubricity using a variety of bench scale test methods. A diagram of the various testing apparatus can be seen in chart provided by Lucas (attached). The two most popular bench test methods for lubricity are the Ball on Cylinder Lubricity Evaluator (BOCLE), and the High Frequency Reciprocating Rig (HFRR). The BOCLE is commonly used to evaluate the lubricity of fuels or fuel blends but does a poor job of characterizing the lubricity of fuels containing lubricity additives, while the HFRR is commonly used for both the neat fuels and with fuels containing small amounts of lubricity enhancing additives. Lubricity Additives The typical chemical structure of a lubricity additive consists of a polar functional group attached to an oleophilic part Ri. Typical functional groups are carboxylic acid (Acid), carboxylic acid ester (Ester) and carboxylic acid amide (Amide) (Table 1). An ester for northern regions has also been tested that has the same functional group as the regular ester, but with a different oleophilic part for an increased solubility in diesel fuel at cold temperatures (high solubility ester - Hi.Sol.Ester). The market-typical treat rates of these additives to achieve the required lubricity of 460 m in an ULSD range from 50 ppm to 300 ppm. For our investigations four different commercial lubricity additives were selected. They comprise an acid, an ester, an ester designed for regions with extremely cold climates and an amide. All the lubricity additives tested do not contain any other active chemical, like detergents and cetaneimprover.

Table 1

Carboxylic Acid

Carboxylic Acid Ester

Carboxylic Acid Amide

Hydrodesulphurization decreases the lubricity reserve of gas oil by 80 -200 m (HFRR) and theload-carrying capacity by 1500 N in the HiTOM. Model sulphur compounds do not restore thelubricity of a hydrotreated diesel fuel. However, dibenzothiophene can increase the loadcarryingcapacity. Therefore, the removal of sulphurisedcompounds is not the major reason for the loss oflubrication of ultra lowsulphur diesel fuels. 9

The model nitrogen compound 8-hydroxyquinoline improves the lubricity at very low concentrations (20 ppm nitrogen) whereas quinoline and acridineneed a higher concentration (100 ppm nitrogen) for some lubricity improvement. This indicates that the removal of nitrogen containing compounds is likely to result in a diesel fuel with poorer lubricity performance. Different lubricity additive technologies withcarboxylic acid-, ester- and amide based chemistries can increase the lubricity in a variety of base fuels at a concentration of 200 ppm to meet the lubricity requirement according to EN 590. These compounds can also provide protection against adhesive wear by increasing the incipient scuffing load. The load-carrying capacity of ULSD 1 can beincreased by 4500 N by an ester based lubricity additive treat rate of 1000 ppm. The acid based additive can only provide an increase of 2500 N at 1000 ppm treat rate. The ester-based additive (200 ppm) can provide an improvement of the load-carrying capacity by 3000 N at a fuel temperature of 90 C.

Q#7: Answer the followings in case of DHDS and Diesel-Max units: I. II. III. IV. V. H 2 /HCS ratio WABT LHSV Radial spread Peak temperature Across the bed T

DHDS:
I. Hydrogen to hydrocarbon ratio: The H2/HCS ratio in case of DHDS is 150-500. II. Weighted average bet temperature(WABT) calculation of Diesel hydro de-sulfurization unit(1010): Bed 1(kg) 1650 1200 1690 5510 24320 840 Sum= 35210 kg Bed 2(kg) 400 48960 5440 840 Sum= 55640 kg

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Total sum of masses of two beds: Mass percent of bed 1: Mass percent of bed 2:

35210+55640 = 90850kg 35210/90850 = 0.387

55640/90850 = 331:C

0.6124

Average temperature of the bed: WABT: = 0.387*331+0.6124*331 WABT = 128.097+202.7044 WABT = 330:C

III. Liquid hourly space velocity (LHSV) of DHDS Reactor: Density calculation of bed 1: Flow rate of the feed: Mass of bed 1: height of the bed: width of the bed: volumeof the bed: Volume of the bed: =55.375m Density: Density: Density: As, Voidage of the bed 1: So, Density: Density: =636.05*1.1774 =748.88 kg/m
3 3

172.3m /hr 35210 kg 4.795 m 3.3 m

=3.14((3.3) /4)*4.795

=m/v = 35210/55.375 = 636.05 kg/m

3

=17%

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Density calculation of bed 2: Mass of the bed 2: Height of the bed 2: Diameter of the bed 2: Volume of the bed 2: Volume of the bed 2: Volume of the bed 2: Density of the bed 2: Density of thr bed 2: Density of the bed 2: As, Voidage of bed 2: So Density of the bed 2: Density of the bed 2: So, Volume of the bed 1: Volume of the bed 1: Volume of the bed 1: And, Volume of the bed 2: Volume of the bed 2: Volume of the bed 2: = mass of the catalyst bed 2/density of the bed 2 = 55640/1060 = 52.49 m
3

=55640 kg = 7.23 m = 3.3 m

= 3.14((3.3) /4)*7.23 = 61.806 m = m/v =55640/61.806 = 900.236 kg/m

3

= 17%

= 900.236*1.1774 = 1060 kg/m

3

=mass of the catalyst bed 1/density of the bed 1 = 3521/748.88 = 47.016 m

3

Sum of the volumes of two beds: = 47.016+52.49 12

=99.506 m LHSV: LHSV: LHSV:

=flow rate of feed(m /hr)/volume of the bed(m ) = 172.3/99.506 = 1.73/hr

IV. Radial Spread: The radial spread of both the beds in DHDS should always be less than 22:C (design value). V. Peak temperature of Diesel hydro-desulfurization reactor: It is the maximum temperature up to which a reactor can be operated and in DHDS reactor case it is 398:C (design value). VI. Across the bed T:

The T across the bed should not be greater than 42:C, otherwise coking rate will increase.

Diesel-Max:
LHSV of Diesel max unit: Feed flow rate: Mass of the bed 1: Mass of the bed 2: Mass of the bed 3: Mass of the bed 4: Density of bed 1: Density of bed 2: Density of bed 3: Density of bed 4: Volume: = mass / density = 36813/870 = 42.313 m
3

= 148.5m /hr = 36813 kg = 32710 kg = 53400 kg = 53400 kg = 870 kg/m = 893 kg/m
3

=1006 kg/m

= 1006 kg/m

Volume of the bed 1 V1: Volume of the bed 1 V1:

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Volume of the bed 2 V2: Volume of bed 2 V2: Volume of the bed 3 V3: Volume of the bed 3 V3: = 53.08 m Volume of the bed 4 V4: Volume of the bed 4 V4: Total volume of the 4 beds: Total volume of 4 beds: Total volume of 4 beds: LHSV: LHSV: LHSV:

=32710/893 =36.629 m
3

= 53400/1006
3

= 53400/1006 = 52.91 m
3

= V1+V2+V3+V4 = 42.313+36.629+53.08+52.91 = 184.93 m

3

= flow rate of feed(m /hr)/volume of the bed(m ) = 148.5/184.93 = 0.8/hr

Q#8: DieselMax Catalytic Reactor (284-R1) & DHDS Reactor (1010-R1), thermocouples configuration and temperature monitoring philosophy? The temperature measurement is measured in both ways across the reactor, i.e. radially along the catalyst bed as well as circumferential measurement along the bed. To understand the philosophy, we shall discuss the configuration of thermocouples at both reactors. THERMOCOUPLES CONFIGURATION There are catalyst bed thermowells installed in catalyst beds. Thermowells can have one or more than one thermocouple for temperature measurement installed at different. 284-R1

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For Diesel Max Catalytic Reactor (284-R1), there are four catalyst beds in a reactor. Top two beds (Catalyst bed # 1 & 2) helps in de-sulphurization and de-nitrification reactions and other two (Catalyst bed# 3 & 4) helps in olefin saturation, aromatic saturation and hydrocracking (as shown in Fig 2). Radial Spread Measurement is carried out by measuring the inside temperature of catalyst bed along different lengths. Catalyst bed 1 & 2, has the provision for measuring the bed temperature at top, middle and bottom, whereas In Catalyst bed there are four points for radial measurements, i.e. Top, upper middle, lower middle and bottom. The configuration for these thermocouples in thermo well can be easily understood by Fig. 1. In Fig. three couples are inserted in one thermo well, which measure the distributed temperature across the bed and different lengths e.g.

Top Middle Bottom

Guard Catalyst Catalyst Bed 1 DHC-2 Catalyst Bed 2 DHC-2

Top Upper Middle Lower Middle Bottom

Catalyst Bed 3 DHC-8

Catalyst Bed 4 DHC-8

Fig.2

Fig.1

a = 0.15 x ID (at 15% radius) b = 0.5 x ID (at 50% radius) c = 0.85 x ID (at 85% radius) Note: ID = Reactor Internal Diameter CIRCUMFERENTIAL MEASUREMENT: Circumferential measurement is carried out by skin thermocouples. In figure 2, the point of circumferential measurement is shown by x at reactor catalyst bed. Each point has 10 thermocouples which are equally spaced from one another. The separation of two points are fixed and vertical distance is shown as, Catalyst Bed No. 1 & 2: 1.2m (5 points each) Catalyst Bed No. 3 & 4: 1.1m (7 points each) 15

1010-R1 (DHDS) Diesel Hydro Desulfurization reactor, 1010-R1, also follows the same reaction chemistry as dieselmax reactor, except few reactions. This reactor has two beds of catalyst, composed of Ni-Mo, Co-Mo configuration. As discussed before, its temperature is also monitored radially and circumferentially. RADIAL SPREAD MEASUREMENT: It is carried out by thermocouples placed inside the thermowells on catalyst bed. Each bed is monitored at the top and bottom. Both of the catalyst bed have the same configuration of thermocouples at top and bottom, which is shown below: Catalyst Bed 1 & 2: Top: Bottom: 3 thermocouples 19 thermocouples

Guard Catalyst

Top

Catalyst Bed - 1

Bottom

Top

Catalyst Bed - 2

Bottom

These thermocouples are placed at different lengths across the bed radially to measure temperature. As discussed before.

Fig.3 CIRCUMFERENTIAL MEASUREMENT: Circumferential measurement is carried out by skin thermocouples. In figure 3, the point of circumferential measurement is shown by x at reactor catalyst bed. The circumferential measurement is at one point for each bed of catalyst. One point consists of 9 thermocouples.
Philosophy for 284-R1: We know that reaction chemistry of Dieselmax reactor is exothermic, hence the effluent temperature across each bed will increase as the conversion and contact time increases along the bed of catalyst, which is maintained by quenching of H2 gas. Enthalpy change or heat of reaction evolved in a reaction per unit consumption of H2, is given as Desulfurization Denitrification Olefin Saturation Aromatic Saturation 1 1 2 1

Bed # 1, 2: Top and middle radial temperature measurement thermocouples are the same where as it is 1 more in bottom measurement because of the conversion that take place along the catalyst bed. Bed # 3,4: Four Points for temperature measurement, It is critical as it deals with saturation of olefins, aromatics and hydrocracking. As the heats of reactions are high and amount of catalyst loaded is also 16

higher than bed # 1, 2. Therefore it is divided into top, upper middle, lower middle and bottom measurement. Philosophy For 1010-R1: Reactions in DHDS reactor are also exothermic in nature and hence increase the temperature of effluents along the bed of the catalyst. The temperature is assured by quenching of H2 gas. Enthalpy change or heat of reaction evolved in a reaction per unit consumption of H2, is given as Desulfurization Denitrification Olefin Saturation Aromatic Saturation 1 1 2 1

Bed # 1,2: For Top measurement, there are three thermocouples which shows the start of the catalyst distribution is proper or not because it can lead to temperature fluctuations if not distributed properly. As the reaction proceeds and effluents reach the bottom of beds after conversion they evolve heat and increase temperature of bed, they are measured at 19 different points radially by thermocouples, because of severity of reactions for that we need to observe the temperature of bed radially at much point than the top. It helps us to control temperature runaway. Generally, Temperature measurement radially and circumferentially gives us the check for, Proper distribution of reactants Channeling in catalyst bed Conversion trends Catalyst life Temperature run away Weighted Average Bed Temperature Maintainence requirement Turn around planning (if required) Physical feeling, insight reactor

Q#9: Explain phenomena of flooding in fired heaters? Answer: Unburned fuel filling in combustion zone of the fired heater due to insufficient air, this phenomenon is termed as flooding. As the air is not sufficient to burn the fuel, the fuel starts to build up in combustion zone of the radiant section, this situation may lead to an explosion. Reason for Flooding: It is observed commonly due to low excess air operation I fired heaters. This may be encountered because of following reasons,

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O2 analyzers located at wrong location O2 analyzers malfunctioning Removal of O2 analyzer from service Sudden changing in fuel charging with slow response to air intake

Counter measures: If unburned fuel has been flooded in combustion chamber then, Fuel charging must be reduced Combustion and excess air must be adjusted Air should not be allowed to introduce from stack or air dampers

How to monitor flooding: It can be recognize with following observations, Drop in bridge wall temperature with respect to fuel quantity fired Pressure fluctuation in firebox and rapid fluctuations in stack damper Hazy appearance in firebox Abnormal noise from furnace (thumping noise) Drop in process outlet temperature with respect to fuel quantity fired High smoke content could be observed in case of oil firing

Q#10: What is refractory; explain its importance & its types? Refractory Refractory is heat resistant materials used in almost all processes involving high temperatures and/or corrosive environment. These are typically used to insulate and protect industrial furnaces and vessels due to their excellent resistance to heat, chemical attack and mechanical damage. Any failure of refractory could result in a great loss of production time, equipment, and sometimes the product itself. Composition of Refractories Refractories are inorganic, nonmetallic, porous and heterogeneous materials composed of thermally stable mineral aggregates, a binder phase and additives. The principal raw materials used in the production of refractories are: the oxides of silicon, aluminum, magnesium, calcium and zirconium and some non-oxide refractories like carbides, nitrides, borides, silicates and graphite. Classification of Refractories Classification method Chemical composition Examples

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ACID, which readily combines with Silica, Semisilica, Aluminosilicate bases BASIC, which consists mainly of metallic Magnesite, oxides that resist the action of bases Dolomite Chrome-magnesite, Magnesite-chromite,

NEUTRAL, which does not combine with Fireclay bricks, Chrome, Pure Alumina acids nor bases Special End use Method of manufacture Carbon, Silicon Carbide, Zirconia Blast furnace casting pit Dry press process, fused cast, hand moulded, formed normal, fired or chemically bonded, unformed (monolithics, plastics, ramming mass, gunning castable, spraying)

Types of Refractories The various types of refractories are as follows: 1. Fireclay refractories Firebrick is the most common form of refractory material. It is used extensively in the iron and steel industry, nonferrous metallurgy, glass industry, pottery kilns, cement industry, and many others. Fireclay refractories, such as firebricks, siliceous fireclays and aluminous clay refractories consist of aluminum silicates with varying silica (SiO2) content of up to 78 percent and Al2O3 content of up to 44 percent. 2. High alumina refractories Alumina silicate refractories containing more than 45 percent alumina are generally termed as high alumina materials. The alumina concentration ranges from 45 to 100 percent. The refractoriness of high alumina refractories increases with increase in alumina percentage. The applications of high alumina refractories include the hearth and shaft of blast furnaces, ceramic kilns, cement kilns, glass tanks and crucibles for melting a wide range of metals. 3. Silica brick Silica brick (or Dinas) is a refractory that contains at least 93 percent SiO2. The raw material is quality rocks. Various grades of silica brick have found extensive use in the iron and steel melting furnaces and the glass industry. In addition to high fusion point multi-type refractories, other important properties are their high resistance to thermal shock (spalling) and their high refractoriness. The outstanding property of silica brick is that it does not begin to soften under high loads until its fusion point is 19

approached. This behavior contrasts with that of many other refractories, for example alumina silicate materials, which begin to fuse and creep at temperatures considerably lower than their fusion points. Other advantages are flux and stag resistance, volume stability and high spalling resistance.

4. Magnesite Magnesite refractories are chemically basic materials, containing at least 85 percent magnesium oxide. They are made from naturally occurring magnesite (MgCO3). The properties of magnesite refractories depend on the concentration of silicate bond at the operating temperatures. Good quality magnesite usually results from a CaO-SiO2 ratio of less than two with a minimum ferrite concentration, particularly if the furnaces lined with the refractory operate in oxidizing and reducing conditions. The slag resistance is very high particularly to lime and iron rich slags. 5. Chromite refractories Two types of chromite refractories are distinguished: Chrome-magnesite refractories, which usually contain 15-35 percent Cr2O3 and 42-50 percent MgO. They are made in a wide range of qualities and are used for building the critical parts of high temperature furnaces. These materials can withstand corrosive slags and gases and have high refractoriness. Magnesite-chromite refractories, which contain at least 60 percent MgO and 8-18 percent Cr2O3. They are suitable for service at the highest temperatures and for contact with the most basic slags used in steel melting. Magnesite-chromite usually has a better spalling resistance than chrome-magnesite.

6. Zirconia refractories Zirconium dioxide (ZrO2) is a polymorphic material. It is essential to stabilize it before application as a refractory, which is achieved by incorporating small quantities of calcium, magnesium and cerium oxide, etc. Its properties depend mainly on the degree of stabilization, quantity of stabilizer and quality of the original raw material. Zirconia refractories have a very high strength at room temperature, which is maintained up to temperatures as high as 150000C. They are therefore useful as high temperature construction materials in furnaces and kilns. The thermal conductivity of zirconium dioxide is much lower than that of most other refractories and the material is therefore used as a high temperature insulating refractory. Zirconia exhibits verylow thermal losses and does not react readily with liquid metals, and is particularly useful for making refractory crucibles and other vessels for metallurgical purposes. Glass furnaces use zirconia because it is not easily wetted by molten glasses and does not react easily with glass. 7. Oxide refractories (Alumina)

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Alumina refractory materials that consist of aluminium oxide with little traces of impurities are known as pure alumina. Alumina is one of the most chemically stable oxides known. It is mechanically very strong, insoluble in water, super heated steam, and most inorganic acids and alkalies. Its properties make it suitable for the shaping of crucibles for fusing sodium carbonate, sodium hydroxide and sodium peroxide. It has a high resistance in oxidizing and reducing atmosphere. Alumina is extensively used in heat processing industries. Highly porous alumina is used for lining furnaces operating up to 1850 0C. 8. Insulating materials Insulating materials greatly reduce the heat losses through walls. Insulation is achieved by providing a layer of material with low heat conductivity between the internal hot surface of a furnace and the external surface, thus keeping the temperature of the external surface low. Insulating materials may be classified into the following groups: Insulating bricks Insulating castables Ceramic fiber Calcium silicate Ceramic coating

Insulating materials owe their low conductivity to their pores while their heat capacity depends on the bulk density and specific heat. Air insulating materials consist of minute pores filled with air, which have a very low thermal conductivity. 9. Castables and concretes Monolithic linings of furnace sections can be constructed by casting refractory insulating concretes, and stamping lightweight aggregates into place that are suitably bonded. Other applications include the bases of tunnel kiln cars used in the ceramic industry. The ingredients are similar to those insulation materials used for making piece refractories, except that concretes contain either Portland or highalumina cement. 10. Ceramic fiber Ceramic fiber is a low thermal mass insulation material, which has revolutionized furnace design lining systems. Ceramic fiber is manufactured by blending and melting alumina and silica at a temperature of 1800 2000 0C, and breaking the molten stream by blowing compressed air or dropping the molten stream on a spinning disc to form loose or bulk ceramic fiber. The bulk fiber is used to produce various insulation products including blankets, strips, veneering and anchored modules, paper, vacuum formed boards and shapes, ropes, wet felt, mastic cement etc. Fibers are usually produced in two temperature grades based on Al2O3 content. A new product is ZrO2 added alumino-silicate fiber, which helps to reduce shrinkage levels and thereby making the fiber suitable for higher temperatures.

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The characteristics of ceramic fibers are a remarkable combination of the properties of refractories and traditional insulation material. a) b) c) d) e) f) g) h) i) j) Lower thermal conductivity Light weight Lower heat storage Thermal shock resistant Chemical resistance Mechanical resilience Low installation cost Ease of maintenance Ease of handling Thermal efficiency

Q#11: Explain heat distribution in heaters? Answer: When fuel is fired in a heater, the energy evolved can be evaluated to contribute following percentages in different section of heater, Radiant section: Overall, this radiant section contributes about 60% of the total energy obtained by firing any quantity of fuel. Which can be further sub classified as, Flame Radiation Visible flame light waves, 14% Hot Gas Radiation Combustion products, 28% Convection Flue gas flow over tubes, 6% Refractory Reflection Mirror effect, 12%

Convection Section: Overall, this radiant section contributes about 25% of the total energy obtained by firing any quantity of fuel by, Convection phenomenon Flue gases movement from radiant to convection section. No radiations are involved in this section Heat Losses: Overall, losses contribute about 25% of the total energy obtained by firing any quantity of fuel. Flue Gases 13% Refractory losses 2%

Hot Gas Radiation

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In gas radiation, one has to distinguish between the gases which are transparent to radiation and which emit and absorb radiations. All diatomic gases like nitrogen and oxygen are transparent to radiation that means they neither emit nor absorb radiation at low temperatures. Whereas, triatomic gases like CO2, H2O, SO2 absorb and emit radiation to a considerable degree so that they are important in heat exchange Absorption and emission of gases differ from liquids and solids in the following ways. Gases emit and absorb radiation within a narrow band of wavelength and Emission and absorption take place through the body of the gas. No. of modules of a gas is important for radiation. No. of molecules of gas at a given temperature is proportional to partial pressure of gas and size of the body (L) of the gas, where. L = 3.5 (volume / surface area)

Q#12: Explain the difference between TBP Curve and ASTM D-86? True Boiling Pont Distillation The true boiling point distillation is the best representation of the true compositions for a petroleum stream. In this method it is essential to accomplish a good degree of separation between components in order to get the definitive boiling ranges of components. Although there is no one true method present to conduct this type of distillation but ASTM D-2892 and the U.S. Bureau of Mines and Hempel are the most common method used to perform this particular test. The ASTM D-2892 method corresponds to the standard laboratory distillation efficiency referred to as 15/5 that is it is conducted using 15 theoretical stages and with a still reflux ratio of 5:1. It gives a good approximation of the separation that can be expected in an actual distillation column as it tends to separate mixture components relatively sharply in accordance to their boiling points. Products are collected and removed according to their boiling point ranges with further test carried out in order to determine the quality of product received. In order to avoid cracking which distort the measurements of the true components of the sample the test is carried out under reduced pressure for high temperatures although keeping in mind that the true boiling temperatures are always reported at a pressure of 760 mm Hg. For many TBP apparatus the minimum pressure obtainable is 40 mm Hg as a result the highest temperature range is 496 to 526oCwhen corrected to pressure base of 1 atm. Unfortunately, the time required and expense required for this test restricts its use to only a new crude oil sample at PARCO refinery to determine its feasibility with PARCOs refining technology. Alternate test method such as the D-86 method is carried out and using their results the TBP is approximated using co-relations.

ASTM-D 86 and its conversion to TBP:

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The ASTM D-86 method is widely used in petroleum industry to find out the specification of finished products. This test method is run at a pressure of 760 mm Hg considering 1 theoretical stage and no reflux unlike the TBP test methods as a result the test method is designed for the analysis of distillate fuels; it is not applicable to products containing appreciable quantities of residual material. In this method 100 milliliters of sample are distilled and all the distilled vapors are removed from the still and condensed with no reflux to the flask. The condenser tube is cooled using an ice water bath. The light temperatures that boil at temperatures below the condensing temperatures are lost from the product and are considered as loss. Finally a vapor temperature versus volume recovered data is recorded and plotted on a graph. In order to convert ASTM D-86 to TBP various methods can be applied including Raizi, Raizi-Daubert and the most common being the Edmistor and Pollock co-relation. The Edmistor and Pollock which was later revised as the Edmistor and Okamoto co-relation consists of two graphs. The first graph relates the D 86 50% distilled temperature to the TBP 50% distilled temperature. The second graph on the other hand consists various curves relating the D 86 temperature slopes to the TBP temperature slopes for segments of the distillation curves with 0-10% distilled, 30-50%, 50-70%, 70-90% and 90-100% distilled curves. A set back that could be noticed that there is no provision of conversion of other distilled product percentages except the ones mentioned above as a result, those distilled percentages are converted using interpolation methods with commercial simulators. One more important aspect to notice is that the Edmistor and Okamoto method always considers a positive slope for distillation curves. Using the graphs the co-relation first converts the D 86 50% distilled temperature to the TBP 50% distilled temperature and then based on the 50% distilled point, temperature difference for the other distilled point are found using the second graph eventually developing the TBP curve. Given below is one of the graphs used for inter conversion.

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The other method of Raizi and Daubert is based on a different approach from the Edmister and Okamoto co-relations. This method however is known to be inconsistent for some cases as the point by point conversions in some cases predicted negative slopes which are a physical impossibility. For this method the following equation is used in order to determine the TBP from ASTM D-86 test. TTBP = a[TD86]bsgc Where, T= temperature in deg R Sg= stream average specific gravity, API a,b,c= unique constants corresponding to 0,10,20,30,50,70,90 and 95% distillates. Raizi Daubert Equation

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