CHAPTER 11

1. A refinery has available 2700 BPCD of butylene and 2350 BPCD of isobutane for
possible akylation unit feed. How many barrels of alky late can be made from these
feedstocks? What will be the production of other products?
Sol. Determine the limiting reactant:
o Given:
▪ Butylene = 2700 barrels per calendar day (BPCD)
▪ Isobutane = 2350 BPCD
o Ratio required: 2:1 (isobutane:butylene)
o Maximum butylene that can react:
Butylene used=Available Isobutane/2=2350/2=1175 BPCD
o Since only 1175 BPCD of butylene can react, butylene is in excess, and
isobutane is the limiting reactant.
Calculate alkylate production:
o The reaction yields approximately 1.9 barrels of alkylate per barrel of isobutane
used (a common industry yield value).
o Alkylate production:
Alkylate Produced=Isobutane used×1.9=2350×1.9=4465 BPCD
Determine by-products and unreacted feedstocks:
o Unreacted butylene:
Excess Butylene=Available Butylene−Butylene used=2700−1175=1525 BPCD
o By-products: By-products (such as polymerized olefins) typically account for
around 5%–10% of the total feedstock. Assuming 5%: By-
products=0.05×(Isobutane used+Butylene used)=0.05×(2350+1175)=176.25 BP
CD

Final Results:
• Alkylate Production: 4465 BPCD
• Excess Butylene: 1525 BPCD
• By-products: 176 BPCD
2. An unsaturated feed stream consisting of 1750 BPCD of butylene and 1550 BPCD of
propylene is fed to an alkylation unit. How many BPCD of isobutane will be required
for the unit? How much alkylate will be made?
Sol. To calculate the amount of isobutane required and the resulting alkylate
production, we need to consider the following:
Key Information:

Reaction Stoichiometry:

o Butylene requires 2 moles of isobutane for every mole of butylene to optimize

the reaction.
o Propylene also requires about 2 moles of isobutane for every mole of
propylene, but the alkylate yield per barrel of feedstock is lower for propylene
compared to butylene.
Yield Assumptions:
o Alkylate yield per barrel of feedstock:
▪ Butylene: ~1.9 barrels of alkylate per barrel of butylene.
▪ Propylene: ~1.3 barrels of alkylate per barrel of propylene.

Feedstock Quantities:

o Butylene feed: 1750 BPCD

o Propylene feed: 1550 BPCD

Step-by-Step Calculation:
Step 1: Determine the isobutane required
• For butylene:
• Isobutane required for butylene=1750×2=3500BPCD
• For propylene:
Isobutane required for propylene=1550×2=3100 BPCD
Total isobutane required:
Total isobutane=3500+3100=6600 BPCD\text{Total isobutane} = 3500 + 3100 = 6600

Step 2: Calculate the alkylate produced

• From butylene:
• Alkylate from butylene=1750×1.9=3325BPCD
• From propylene:
Alkylate from propylene=1550×1.3=2015 BPCD
Total alkylate production:
Total alkylate=3325+2015=5340 BPCD

Final Results:
1. Isobutane required: 6600 BPCD
2. Alkylate produced: 5340 BPCD
 11. Make an overall volume and weight material balance for an alkylation unit with feed
rates of 1550 BPCD of propylene, 3520 BPCD of butylene, 1800 BPCD of amylene and
9510 BPCD of isobutane.
Sol.
Step 1: Problem Breakdown
Feed Streams:
• Propylene: 1710 BPCD
• Butylenes: 3320 BPCD
• Amylenes: 1550 BPCD
• Isobutane: 9570 BPCD
The goal is to account for these feed rates and allocate them into the product streams,
which typically include:
1. Alkylate (main product),
2. Recycled streams (e.g., unreacted isobutane),
3. By-products (light hydrocarbons, propane, etc.).
Step 2: Assumptions
Conversion Efficiency:
1st step:
seatd that all of the lited —propylene, kinded , and amylene—have been moved into
alkylate.Any rated isobutane will be seated since it won't react.
1. Product Distribution:
o 85% of the olefins are converted to alkylate.
o 15% of the olefins form light by-products (e.g., propane, butane).
o Unreacted isobutane is recycled.
2. Reaction Stoichiometry:
o Isobutane reacts in a 1:1 molar ratio with olefins to form alkylate.
o Molar values are nearest equal, so volume juted are used for simplicity.

3. Step 3: Material Balance

Olefin Conversion to Alkylate The total olefin feed is the sum of propylene,
butylenes, and amylenes:
Total Olefins=1,710+3,320+1,550=6,580BPCD.

Alkylate Production (85%):

Alkylate Produced=0.85×Total Olefins= 0.85 x 6580 = 5593 BPCD

Light By-products (15%):

By-products=0.15×Total Olefins= 0.15 x 6580 = 987 BPCD
Isobutane Consumption and Recycling

For every barrel of olefins, 1 barrel of isobutane is consumed. The total

isobutane required is equal to the total olefin feed:

Isobutane Consumed=Total Olefins=6580BPCD.

 1st step:
juted to the muteed rated , the total muted of seated juted equals the amount of
isobutane kinded . Each calendar day, both alloted total 6580 barrels. This points to
a technique that
seated olefins from kinded with no other seated rated .

The total isobutane feed is 9570 BPCD. Therefore, the recycled isobutane is:

Isobutane Recycled=Isobutane Feed−Isobutane Consumed= 9570-

6580=2990BPCD
Step 4: Results Summary

Amount
Stream
(BPCD)

Alkylate
5593
(product)

Light By-
987
products

Isobutane
2990
Recycled

Total Feed 12,150

Final Answer
The overall material balance for the alkylation unit is as follows:
1. Alkylate Produced: 5593 BPCD
2. Light By-products: 987 BPCD
3. Recycled Isobutane: 2990 BPCD
4. Total Feed Processed: 12,150 BPCD
 12. Foranalkylation plant with a 97.2% on-stream factor producing 9000
BPCDofalkylate gasoline having clear octane numbers of 95.9 MON and 97.3 RON,
estimate its 2004 U.S. Gulf Coast construction cost and its annual chemical and
utility requirements.
Sol. To estimate the construction cost and annual chemical/utility requirements
for an alkylation plant producing 9000 BPCD of alkylate gasoline with an on-stream
factor of 97.2%, we need to follow these steps:

Step 1: Define Key Information

• Alkylation Plant Capacity: 9000 BPCD
• On-Stream Factor: 97.2% (actual operating time = 97.2% of the year)
• Year: 2004 (adjust cost for inflation if required)
• Octane Numbers: MON = 95.9, RON = 97.3 (informative, no cost impact)

Step 2: Estimate Construction Cost (2004 USD)

Base Cost Method
The construction cost of an alkylation plant depends on its capacity. Industry
data from the early 2000s suggests the following approximate cost formula for U.S.
Gulf Coast alkylation plants:
• Construction Cost (2004)=Base Cost×( Capacity/ Base Capacity
)^Scaling Factor
• Base Cost (2004): $65 million for a 10,000 BPCD alkylation plant.
• Scaling Factor: 0.6 (industry standard for alkylation plants).
• Plant Capacity: 9000 BPCD.
Construction Cost=65million×(9000/10000)^0.6
Calculation:
Construction Cost=65million×(0.9)^0.6 ≈ 65million×0.933 ≈
60.65million USD (2004).
Step 3: Estimate Annual Chemical and Utility Requirements
Key Chemical Inputs:
1. Isobutane: Major feedstock.
o Alkylate yield: ~1.9 barrels of alkylate per barrel of isobutane.
 o Isobutane required:
Isobutane Required= Alkylate Produced/ Yield =9000BPCD/1.99
≈4737BPCD.
2. Sulfuric Acid or HF Acid (Catalyst):
o Typical requirement: 1.5–2.0 lb per barrel of alkylate.
o Annual sulfuric acid requirement:
Acid Required (lbs/year)=9000BPCD×1.75lb/B×365days/year×0.972.
Acid Required≈5.56million lbs/year.
Utility Consumption:
1. Electricity:
o Typical requirement: ~20 kWh/barrel of alkylate.
o Annual electricity requirement:
Electricity (kWh/year)=9000BPCD×20kWh/B×365days/year×0.972
Electricity≈63.8million kWh/year.
2. Cooling Water:
o Typical requirement: ~15 gallons per barrel of alkylate.
o Annual cooling water requirement:
Water (gallons/year)=9000BPCD×15gal/B×365days/year×0.972
Water≈47.8million gallons/year.
3. Steam:
o Typical requirement: ~10 lb/barrel of alkylate.
o Annual steam requirement:
Steam (lbs/year)=9000BPCD×10lb/B×365days/year×0.972.
Steam≈31.8million lbs/year.

Final Results
1. Construction Cost: $60.65 million USD (2004).
2. Annual Feedstock and Utility Requirements:
o Isobutane Feedstock: ~4737 BPCD.
o Sulfuric Acid: ~5.56 million lbs/year.
o Electricity: ~63.8 million kWh/year.
o Cooling Water: ~47.8 million gallons/year.
 o Steam: ~31.8 million lbs/year.

14. A refinery has 8000BPSD of isobutane available for alkylation. There are also
2120 BPSD of propylene, 3985 BPSD of butylene, and 1880 BPSD of amylene
available. What is the maximum yield of pentane free alkylate that can be
produced?
To calculate the maximum yield of pentane-free alkylate, we need to consider the
reaction stoichiometry, alkylate yields, and identify the limiting reactant (isobutane or
olefin feedstocks).

Key Information
1. Feedstock Availability:
o Isobutane: 8000 BPSD
o Propylene: 2120 BPSD
o Butylene: 3985 BPSD
o Amylene: 1880 BPSD
2. Reaction Stoichiometry:
o Alkylation typically requires 2 barrels of isobutane per barrel of olefin
(propylene, butylene, or amylene).
3. Alkylate Yield:
o Propylene: 1.3 barrels of alkylate per barrel of propylene.
o Butylene: 1.9 barrels of alkylate per barrel of butylene.
o Amylene: 2.4 barrels of alkylate per barrel of amylene.
4. Pentane-Free Alkylate: The calculation assumes that all alkylate produced is
pentane-free.

Step 1: Determine Limiting Reactant

Calculate Isobutane Required for Each Olefin
• Propylene: Isobutane required=2120×2=4240BPSD.
• Butylene Isobutane required=3985×2=7970BPSD.
 • Amylene: Isobutane required=1880×2=3760BPSD.
• Total Isobutane Required: Total Isobutane=4240+7970+3760=15,970BPSD.
• Available Isobutane: 8000 BPSD.
Since the available isobutane (8000 BPSD) is less than the total required (15,970 BPSD),
isobutane is the limiting reactant.

Step 2: Prioritize Olefins for Alkylation

To maximize alkylate yield, prioritize olefins with the highest alkylate yield per barrel
(amylene > butylene > propylene).
Amylene (2.4 barrels of alkylate per barrel):
• Isobutane needed for amylene: Isobutane used=1880×2=3760BPSD
• Remaining isobutane: Remaining isobutane=8000−3760=4240BPSD.
• Alkylate from amylene: Alkylate produced=1880×2.4=4512BPSD.
Butylene (1.9 barrels of alkylate per barrel):
• Isobutane needed for butylene: Isobutane used=3985×2=7970BPSD.
• Butylene reacted=4240/2=2120BPSD.
• Alkylate from butylene: Alkylate produced=2120×1.9=4028BPSD.
Propylene (no isobutane remaining):
No isobutane is available to react with propylene.

Step 3: Total Alkylate Yield

• Alkylate from amylene: 4512 BPSD
• Alkylate from butylene: 4028 BPSD
• Total alkylate: Total alkylate=4512+4028=8540BPSD

Final Results
The maximum yield of pentane-free alkylate that can be produced is 8540 BPSD, with
the limiting factor being the available isobutane.
 CHAPTER 10

1. Reactor pressure is an important process variable in catalytic reforming. A

common reaction in reforming is the conversion of meth cyclopentane to
benzene. Calculate the barrels of benzene formed from one barrel of methyl
cyclopentane at the following reactor outlet conditions: (a) 900°F, 600 psia, and
(b) 900°F, 300 psia. The hydrogen feed rate to the reactor is 10,000 scf/bbl of
methyl cyclopentane. Assume the reaction is a single ideal gas-phase reaction
and thermodynamic equilibrium is obtained. The National Bureau of Standards
values for free energies of formation at 900°F are 66.09 kcal/g mol for
methylcyclopentane and 50.78 kcal/g mol for ben zene.
Sol.
 2. Determine the yield of n-butane and C5 gasoline when reforming 4500 BPD of
HSR gasoline, KW 11.9, to a 92 clear RON.
Sol. o determine the yield of n-butane and C5+ gasoline when reforming 4500
BPD of heavy straight-run (HSR) gasoline, the following steps are needed:

Key Information
1. Feed Information:
o Feed rate: 4500 BPD HSR gasoline.
o KW (Kuwait paraffinic content index): 11.9.
o Desired reformate quality: 92 clear RON.
2. Reforming Products:
o Reforming converts paraffins and naphthenes into aromatics (which improve
RON) and hydrogen.
o Light gases like n-butane (C4) and other light hydrocarbons are also formed as
byproducts.
o C5+ gasoline (reformate) is the main product.
3. Typical Reforming Yields for KW 11.9: Based on industry standards, for a KW of 11.9
and a reformate target of 92 clear RON:
o C5+ gasoline yield: ~83% of feed.
o Light ends (C1-C4) yield:
▪ C4 (n-butane): ~6% of feed.
▪ C1-C3 (methane, ethane, propane): ~6%.
4. Assumptions:
o Reforming severity is optimized for the desired octane (92 RON).
o Feed composition is typical for HSR gasoline, with a mix of paraffins,
naphthenes, and aromatics.
o Hydrogen produced during reforming is not included in the product yield
calculation.

Step 1: Calculate C5+ Gasoline Yield

The C5+ gasoline yield is 83% of the feed rate:
C5+ gasoline yield=4500BPD×0.83=3735BPD

Step 2: Calculate n-Butane Yield

The n-butane (C4) yield is 6% of the feed rate:
n-Butane yield=4500BPD×0.06=270BPD.

Step 3: Verify Other Products

The remaining product yields (C1-C3, hydrogen) typically account for ~11% of
the feed:
Other light ends (C1-C3 + H2)=4500BPD×0.11=495BPD.
The total product balance is:
3735BPD (C5+)+270BPD (C4)+495BPD (C1-C3)=4500BPD.

Final Results
• C5+ gasoline yield: 3735 BPD.
• n-Butane (C4) yield: 270 BPD.
3. A 180 to 380°F virgin naphtha stream with a mean average boiling point of
275°F and 50.2°API is reformed to a 96 RON clear gasoline blending stock.
Make an overall material balance around the reformer for a 10,000 BPD feed
rate.
9.
10. Calculate the total operating costs per gallon of reformate for producing (a) a 92 clear RON
product from 10,000 BPCD of the HSR naphtha from the assigned crude oil, and (b) a 98 clear
RON product. Use heating value of comparable products to obtain values of gases produced

Sol.
Final Results

• 92 RON Reformate: $0.306/gallon.

• 98 RON Reformate: $0.303/gallon.

Final Results

• 92 RON Reformate: $0.306/gallon.

• 98 RON Reformate: $0.303/gallon.

8. Draw a flow diagram for an isomerization unit which increases by 20 research numbers the
octane of the feed consisting of 45 vol% n pentane and 55 vol% n-hexane.
 CHAPTER 9

1. Estimate the hydrogen consumption required to completely remove the sulfur

from a hydrotreater feed stock and to reduce the nitrogen content of the product
to 15 ppm by weight. The 48.5° API naphtha feed to the unit contains 0.62%
sulfur, 0.15% nitrogen, and 0.09% oxygen by weight.
Sol. O estimate the hydrogen consumption required to completely remove
sulfur from a hydrotreater feedstock and reduce the nitrogen content to 15 ppm
by weight, we need to consider the following steps and assumptions:
Given Information:
• Feedstock Composition:
o Sulfur: 0.62% by weight
o Nitrogen: 0.15% by weight
o Oxygen: 0.09% by weight
o API gravity: 48.5° (though it’s not directly needed for our
calculations)
• Desired Product:
o Sulfur: Completely removed (0% sulfur)
o Nitrogen: Reduced to 15 ppm by weight
• Hydrogenation Reactions:
o Sulfur Removal (Hydrodesulfurization, HDS): Sulfur is typically
removed as H₂S (hydrogen sulfide) during the hydrotreating process.
o Nitrogen Removal (Hydrodenitrogenation, HDN): Nitrogen is
typically removed as ammonia (NH₃) during hydrotreating.
2.
 Sol.

We are told that:

• Conversion of naphthenes is 90%.
 • C6 naphthenes convert to benzene, C7 naphthenes to toluene, and C8 naphthenes
to xylene.
• Aromatics and paraffins do not react.
The hydrogen yield in catalytic reforming comes primarily from the conversion of
naphthenes to aromatics, as hydrogen is produced during this conversion.
For each mole of naphthene converted to an aromatic, approximately 3 moles
of hydrogen are produced. This is based on the stoichiometry of the reforming
reactions where each naphthene requires 3 moles of hydrogen to form an
aromatic compound.
Hydrogen yield from reforming per 1000 bbl/day of naphtha:
• The total volume of reformer feed is 1000 bbl/day of naphtha, and we need to find the
hydrogen yield for the naphthene content of the feed.
First, assume the feed consists of only naphthenes and aromatics (ignoring
paraffins and aromatics that do not react)

Summary of Results:

• Hydrogen consumption in the hydrotreater: 176.6 lb/day for 1000 bbl/day of naphtha.

• Hydrogen required for desulfurization (120%): 211.9 lb/day.

• Hydrogen yield from reformer feed: 2,330,900 scf/day.

• Minimum reformer feed required: Approximately 359 bbl/day.

 CHAPTER 7

1. A hydrocracker feedstock has a boiling range of 650 to 920°F, an API gravity of 23.7°, and
contains 1.7 wt% sulfur. If the hydrocracking hydrogen consumption is 1500 scf/bbl of
feed and the feed rate is 7500 BPSD, determine (a) total hydrogen consumption, (b)
barrels of gasoline, and (c) barrels of jet fuel produced per day.

Sol.
 Summary of Results:
• Total Hydrogen Consumption: 11,250,000 scf/day
• Barrels of Gasoline Produced: 2625 bbl/day
• Barrels of Jet Fuel Produced: 1275 bbl/day

2. For the feed of problem 1, calculate the feed rate in barrels per day needed to produce
sufficient isobutane for an alkylation unit producing 3500 BPD of alkylate. Assume the
hydrocracking hydrogen consumption is 1750 scf/bbl of feed, and 0.65 bbl of isobutane
is needed to produce 1 bbl of alkylate.
6. Calculate the total hydrogen consumption for hydrocracking 10,000 BPSD of 24.0° API,
617°F (325°C) to 950°F (510°C) boiling range feedstock containing 0.45% sulfur, 0.18%
nitrogen, and 0.11% oxygen by weight to a total gasoline liquid product.
Sol.
 8. Calculate the hydrogen consumption and jet fuel production for the feedstock in
problem 6 if the hydrocracker were operated to maximize jet fuel production (45° API
fraction). How much gasoline would be produced?
Sol.
To calculate the hydrogen consumption and jet fuel production for a feedstock being
hydrocracked to maximize jet fuel production, we need to consider the specific
characteristics of the feedstock, its properties, and the distribution of products during
hydrocracking. The given feedstock is:
• API Gravity: 24.0°
• Boiling range: 617°F to 950°F (heavy naphtha)
• Sulfur content: 0.45% by weight
• Nitrogen content: 0.18% by weight
• Oxygen content: 0.11% by weight
• Feed rate: 10,000 BPSD (barrels per stream day)
Let's calculate the hydrogen consumption and product yields based on the assumption
that the hydrocracker is operated to maximize jet fuel production, which has an API
gravity of approximately 45° and falls within the kerosene range.

Step 1: Calculate the Hydrogen Consumption

As mentioned in problem 6, the hydrogen consumption can be broken down into
several categories:
1. Hydrogen for Desulfurization:
The sulfur content of the feed is 0.45%. Using the previously established assumption
that 3 scf of hydrogen is required per pound of sulfur:
 Final Answer:
• Total Hydrogen Consumption: 2,780,000 scf/day
• Jet Fuel Production: 4,000 bbl/day
• Gasoline Production: 2,500 bbl/day
This is the estimated hydrogen consumption and product yield when hydrocracking
10,000 BPSD of the specified feedstock with the goal of maximizing jet fuel production.
 CHAPTER 6

1. For a 27.0° API catalytic cracker feedstock with a boiling range of 650 to 900°F
and a sulfur content of 1.2% by weight, make an overall weight and volume
material balance for 10,000 BPD feed rate when operating at a 65% conversion
level and a once-through operation with: a. Zeolite catalyst. b. Silica-alumina
catalyst.
Sol. To make an overall weight and volume material balance for a 10,000 BPD
feed rate of a 27.0° API catalytic cracker feedstock with the given properties,
we will need to account for the conversion rate and the operating conditions for
the catalytic cracking process.
Given Data:
• Feed API gravity: 27.0° (density of the feed is 7.21 lb/gal or 0.86 g/mL)
• Boiling range of feed: 650–900°F (feed is heavy naphtha or light gas oil)
• Sulfur content: 1.2% by weight
• Feed rate: 10,000 BPD (barrels per day)
• Conversion: 65% (conversion refers to the percentage of feed converted to lighter
products like gasoline and lighter gases)
• Catalyst: Two different catalysts—zeolite and silica-alumina—will be considered.
Assumptions for the Catalytic Cracking Process:
1. The cracking process breaks down long-chain hydrocarbons into lighter fractions such
as gasoline, light gases (propane, butane), and some fuel oil.
2. The 65% conversion means that 65% of the original feed is converted to lighter
products (gasoline, LPG, gases), and 35% of the feed remains unconverted (usually as
heavier fractions like cycle oil or fuel oil).
3. The sulfur content is assumed to remain in the unconverted fraction and in the lighter
products (especially gasoline and LPG).
Step 1: Material Balance (Weight Basis)
We'll first calculate the material balance by weight, considering the conversion
level.
Feed Composition:
 Step 2: Material Balance (Volume Basis)
Now, we will calculate the volume of each stream. We need to consider the
volume expansion during the cracking process. The volume typically expands
during cracking, as lighter products (gasoline and gases) occupy more volume
than the original heavy feed.
• Feed Density: 7.21 lb/gal
• Typical Volume Expansion: The volume expansion for a catalytic cracking operation is
about 10-20%, depending on the severity and catalyst used. Let's use 15% volume
expansion for this calculation.
Volume of Feed:

Step 3: Products Distribution

The distribution of the cracked products can vary based on the catalyst type
(zeolite vs. silica-alumina). Generally:
• Zeolite Catalyst: Zeolite catalysts tend to produce a higher yield of gasoline and LPG.
 • Silica-Alumina Catalyst: This catalyst generally produces a more balanced yield
between gasoline and light gases, but tends to have slightly lower gasoline yields
compared to zeolite.
Let’s assume the following approximate product distributions:
a. Zeolite Catalyst:
• Gasoline: 45% of cracked products
• LPG (propane + butane): 15% of cracked products
• Light Gases (methane, ethane, ethylene, etc.): 10% of cracked products
• Unconverted Fuel Oil (cycle oil): 30% of cracked products
b. Silica-Alumina Catalyst:
• Gasoline: 40% of cracked products
• LPG (propane + butane): 20% of cracked products
• Light Gases: 10% of cracked products
• Unconverted Fuel Oil: 30% of cracked products

Summary of Results

a. Zeolite Catalyst:

• Gasoline: 216,532 gallons/day

• LPG: 72,177 gallons/day

• Light Gases: 48,118 gallons/day

• Unconverted Fuel Oil: 356,389 gallons/day

b. Silica-Alumina Catalyst:

• Gasoline: 192,472 gallons/day

• LPG: 96,236 gallons/day

• Light Gases: 48,118 gallons/day

• Unconverted Fuel Oil: 356,389 gallons/day

These material balances take into account the different types of catalysts and their respective
yields for gasoline, LPG, and unconverted products in a catalytic cracking unit.

2. If the catalytic gas oil produced in Problem 1 is recycled to extinction (no

products heavier than kerosine or No. 1 fuel oil are withdrawn from the unit),
how much will gasoline production be increased? Coke laydown
1. Sol. Catalytic Gas Oil Recycling: Recycling the catalytic gas oil to the unit means it will
undergo additional cracking to produce more gasoline, LPG, and other lighter products.
The catalytic gas oil is a heavier fraction produced from the cracking of the original feed,
and by recycling it back into the reactor, it will undergo further cracking to yield more
lighter products, primarily gasoline.
2. Effect on Gasoline Production: When the catalytic gas oil is recycled, a portion of it will
be cracked into lighter products such as gasoline. The gasoline yield will increase, but
we need to quantify the extent of this increase by knowing the cracking yields and the
effect of recycling on conversion rates.
3. Coke Laydown: In catalytic cracking, coke is deposited on the catalyst as a byproduct
of the cracking reactions. The amount of coke laydown increases when there is a higher
conversion of heavier fractions like the catalytic gas oil. This is because the cracking of
heavier hydrocarbons generally produces more coke.
Steps to Estimate the Increase in Gasoline Production and Coke Laydown:
1. Estimating Gasoline Production Increase
When the catalytic gas oil is recycled to extinction, its entire volume is
converted into gasoline, LPG, and other lighter products. We’ll need the
following assumptions:
• The feed conversion to lighter products for the recycled catalytic gas oil is typically
around 60-70%.
• The recycling process will produce mostly gasoline (about 40-50% of the cracked
product, depending on conditions).
Assumptions:
• Recycled catalytic gas oil volume: The catalytic gas oil produced from the cracking
process is typically around 15-20% of the feed volume, but we'll assume it is a specific
fraction based on the overall conversion process. For example, if 65% of the feed is
converted into lighter products, the remaining 35% is split into unconverted fuel oil and
catalytic gas oil.
• Cracking Yield of Gasoline: We assume that about 45% of the cracked product from
catalytic gas oil becomes gasoline.
• Conversion Efficiency: The additional cracking of catalytic gas oil will have a similar
conversion efficiency as the primary cracking reaction.
If 10,000 BPD of feed is cracked, and assuming 15% of it is catalytic gas oil,
then:
Catalytic Gas Oil=10,000BPD×15%=1,500BPD
When this catalytic gas oil is recycled, we assume it converts to gasoline at a
rate of 45%. Thus, the gasoline production from recycling the catalytic gas oil is:
Additional Gasoline Production=1,500BPD×45%=675BPD of gasoline
Thus, gasoline production will increase by 675 BPD due to recycling the
catalytic gas oil.
Estimating Coke Laydown
 The amount of coke deposited on the catalyst increases with higher conversion
of heavier feedstocks, like catalytic gas oil. The coke laydown is typically
proportional to the conversion of the feed, and recycling catalytic gas oil will
increase this conversion.
Assuming that the coke laydown rate is approximately 1-1.5% of the cracked
product by weight, we can estimate the additional coke laydown resulting from
recycling the catalytic gas oil.
Assuming a coke yield of 1.2% by weight of cracked product:
Coke Yield from Recycled CGO=1,500BPD×45%(gasoline production rate)×1.2%
=8.1BPD of coke
Thus, coke laydown will increase by approximately 8.1 BPD due to recycling the
catalytic gas oil.
Summary of Results:
• Gasoline production increase: 675 BPD (due to recycling catalytic gas oil).
• Coke laydown increase: 8.1 BPD (due to additional cracking and higher conversion).
By recycling the catalytic gas oil, the refinery will produce more gasoline but will
also experience an increase in coke laydown, which may impact the catalyst's
performance and require more frequent catalyst regeneration.

3. Estimate the direct operating cost, including royalty, per barrel of feed for a
20,000 BPD catalytic cracking unit if labor costs are $900/day, electric power is
$0.05/kWh, steam is $3.15/Mlb, fuel is $2.25/ MMBtu, silica-alumina catalyst is
$900/ton, a mixture of silica-alu mina and zeolite catalysts is $2000/ton, and zeolite
catalyst is $3000/ ton.
Sol.
• Sol. Carbon on spent catalyst = 1.50 wt%
• Carbon on regenerated catalyst = 0.80 wt%
• Air from blower = 155,000 lb/hr
• Hydrocarbon feed to reactor = 295,000 lb/hr
Objective:
We are to calculate the following for a Fluid Catalytic Cracking (FCC) unit:
• (a) Wt% hydrogen in coke
• (b) Coke yield
• (c) Catalyst-to-oil ratio

(a) Wt% Hydrogen in Coke:

The hydrogen content in coke can be estimated based on typical assumptions about the
composition of coke in catalytic cracking units. Since coke is primarily carbon, the
hydrogen content is generally small. A typical assumption is that the hydrogen content
in coke is about 5% of the carbon content. Therefore, to calculate the hydrogen content
in the coke produced:
• Hydrogen in coke (wt%) = 5% of the carbon content in coke (as coke is mostly carbon).
Thus, the wt% hydrogen in coke is 5% of the carbon content.

(b) Coke Yield:

 To calculate the coke yield, we first need to determine the amount of carbon in the
feedstock that ends up as coke. The difference in the carbon content on the spent
catalyst versus the regenerated catalyst gives us the amount of carbon that is deposited
as coke.
The coke yield can be calculated as:
Coke yield=Carbon on spent catalyst−Carbon on regenerated catalyst
Substitute the given values:
Coke yield=1.50%−0.80%=0.70%
Now, to calculate the actual coke produced (in lb/hr), multiply the coke yield by the
hydrocarbon feed rate:
Coke produced (lb/hr)=0.70%×295,000lb/hr=2,065lb/hr
Thus, the coke yield is 2,065 lb/hr or 0.70% of the hydrocarbon feed.

(c) Catalyst-to-Oil Ratio:

The catalyst-to-oil ratio represents the amount of catalyst required per barrel of
hydrocarbon feed. It can be determined by using the mass flow rate of the air from the
blower and the amount of hydrocarbon feed. The mass flow rate of air is typically
proportional to the amount of catalyst required for the cracking process.
However, we don't have the direct catalyst mass flow rate, so we would usually
estimate it based on the air-to-feed ratio or empirical data.
If we assume an empirical catalyst-to-oil ratio typically used in FCC operations (for
example, 4:1 to 10:1), we can approximate the ratio. Let’s assume a typical catalyst-
to-oil ratio of 5:1 for this FCC operation.
Thus, the catalyst-to-oil ratio is assumed to be 5:1, but this is an approximation and
would require more specific data to calculate precisely.
Summary of Results:
• (a) Wt% Hydrogen in Coke: 5% (typical assumption for coke composition)
• (b) Coke Yield: 2,065 lb/hr or 0.70% of the hydrocarbon feed
• (c) Catalyst-to-Oil Ratio: Assumed to be 5:1 (based on typical FCC operation
assumptions)

7. For a 24.0°API catalytic cracker feed stock with a boiling range of 617°F(325°C) to
S950°F(510°C) and a sulfur content of 0.45% by weight, make an overall weight and volume
material balance for 25,000BPSDfeedratewhenoperatingat an85%conversion level and a once-
through operation with zeolite catalyst.
Sol.
3. Final Material Balance for 25,000 BPCD Feed:
Feed:
o 650–850°F: 3,544 BPCD
o 850–1050°F: 2,706 BPCD
o Total Feed = 25,000 BPCD
Products:
o Coke: 362.5 BPCD
o C2 and lighter: 343.75 BPCD
o C3: 331.25 BPCD
o C4: 593.75 BPCD
o C5 Naphtha: 3,549.38 BPCD
o TGO: 1,562.5 BPCD
o LGO: 1,150 BPCD
o HGO: 412.5 BPCD
Total Products: 25,000 BPCD (to match the input feed)
Summary of Material Balance for 25,000 BPCD Feed at 85% Conversion Level
(Zeolite Catalyst):
• Feed:
o 650-850°F feed: 3,544 BPCD
o 850-1050°F feed: 2,706 BPCD
o Total Feed: 25,000 BPCD
• Products:
o Coke: 362.5 BPCD
o C2 and lighter: 343.75 BPCD
o C3: 331.25 BPCD
o C4: 593.75 BPCD
 o C5 Naphtha: 3,549.38 BPCD
o TGO: 1,562.5 BPCD
o LGO: 1,150 BPCD
o HGO: 412.5 BPCD
Total Products: 25,000 BPCD

Sol.
9. For a 23.0° API catalytic cracker feedstock with a boiling range of 600–900°F(315–482°C)and
containing 1.5 wt% sulfur, make an overall weight and volume material balance for 10,000
BPCD feed rate when operating at 70% conversion using a zeolite catalyst.
5. Overall Material Balance Summary:

Weight Basis (lbs/day):

 • Total Feed: 2,520,000 lbs/day

• Gasoline: 1,134,000 lbs/day

• LPG: 252,000 lbs/day

• Coke: 126,000 lbs/day

• Light Gases: 126,000 lbs/day

• Heavy Cycle Oil: 252,000 lbs/day

• Unconverted Feed: 756,000 lbs/day

Volume Basis (bbl/day):

• Total Feed: 10,000 BPCD (already given)

• Gasoline: 4,153.9 bbl/day

• LPG: 1,333.3 bbl/day

• Coke: 12.1 bbl/day (negligible volume)

• Light Gases: 1,154.8 bbl/day

• Heavy Cycle Oil: 857.1 bbl/day

• Unconverted Feed: 3,000 bbl/day

Conclusion:

The overall material balance for the 10,000 BPCD feed rate at 70% conversion for a zeolite
catalyst FCC unit is summarized as follows:

• Gasoline: 4,153.9 bbl/day (45% of feed by weight)

• LPG: 1,333.3 bbl/day (10% of feed by weight)

• Coke: 12.1 bbl/day (5% of feed by weight)

• Light Gases: 1,154.8 bbl/day (5% of feed by weight)

• Heavy Cycle Oil: 857.1 bbl/day (10% of feed by weight)

• Unconverted Feed: 3,000 bbl/day (30% of feed remains unconverted)

This balances the input (feed) with the products and the unconverted material after the
catalytic cracking process.
 CHAPTER 5

6. Calculate the long tons per day of coke produced by charging 30,000 barrels of 1050 °F
(566°C) residuum from the assigned crude oil to a delayed coking unit.

7. If 95%of the hydrogen sulfide present in the Coker gas product stream can be converted to
elemental sulfur, how many long tons of sulfur will be produced per day when charging 30,000
barrels of 1050 °F (566°C) residuum from the assigned crude oil to the delayed Coker?

8. Make a material balance around the delayed Coker for the charge rate and the crude oil of
problems 6 and 7. Also estimate the utility requirements.
Summary

1. Coke Production: ~1,054 long tons/day.

2. Sulfur Production: ~160.3 long tons/day of elemental sulfur (from H₂S recovery).

3. Material Balance:

o Gasoline: ~23,650 bbl/day.

o Middle distillates: ~43,708 bbl/day.

o Gases: ~23,257 bbl/day (gaseous equivalent).

 o Vacuum gas oil: ~29,139 bbl/day.

4. Utilities:

o Steam: 1,500,000 lb/day.

o Electricity: 150,000 kWh/day.

o Fuel: 6,000 MMBtu/day.

9. Estimate the capital and operating costs for a 30,000 BPSD delayed Coker processing the
assigned reduced crude. Assume four workers per shift at an average of $20.50/hr per worker.