PACKED BED REACTORS

FIXED BED REACTOR MOVING BED REACTOR

- most common type of multiphase catalyst reactor - the catalyst bed is moving in the
- catalyst does not move reactor
Advantages - used for system with catalysts that are
- simple and robust design because no moving parts, the moving part will increase complexity and decrease deactivated and regenerated quickly
reliability Advantages
- efficient contacting due to tightly packed, hence process highest catalyst loading per reactor volume and able to -catalysts can be removed and
achieve plug flow regenerated
Shortcomings Shortcomings
- cannot use small sizes of catalyst because will cause plugging and high pressure drop -catalyst size must be uniform for
- very difficult to unload and regenerate catalyst smooth flow
- non-isothermal behaviour - require large particle size like fixed
- leads to non-uniform product formation bed
- poor heat conductivity cause difficult temperature control, because the hot spots might develop in highly - could also cause hot spot
exothermic reactions and lead to thermal runaway (hot spot can be reduced by using coolant or further - limited to lower pressure system
intercooling via heat exchanger) Applications
- may have catalyst bed channelling which will cause inefficient contact and therefore low conversion (good - UOP CCR Platforming (increase
dispersion can be achieved by means of distributor such as perforated plate or sintered plate of porous materials) RON)
Types
- Trickle-bed reactor (liquid down and surround the catalyst & gas surround the liquid film), sometimes may have
liquid maldistribution, because gas can distribute evenly but liquid cannot, because liquid does not go through the
catalyst
Applications
- Sasol Fischer Tropsch (FT) process

DISPERSED REACTOR
FLUIDIZED BED REACTOR SLURRY REACTOR STARIGHT-THROUGH-
TRANSPORT REACTOR
- an upward-flowing stream of fluid (gas or liquid) is passes - semiliquid mixture, fine particles - for system with catalyst that are
through a granular solid material (catalyst) at high enough velocity suspended in liquid deactivated very quickly
to suspend the solid and cause it to behave as through it were a - catalyst is suspended in the liquid, and gas -catalyst and reactant enter together are
fluid exist in the form of bubbles transported very rapidly through the
- most of the case is involve gas-solid - may be operated in semi batch or reactor (usually travel at same speed)
continuous mode -bulk density of catalyst pellets are
Fixed bed: gas flow rate is not enough to achieve fluidization - usually used when size of catalysts particle significantly smaller than in moving-bed
is an important factor and dispersion of heat reactors
Incipient or minimum fluidization: gas flow rate increases is important Applications
beyond minimum fluidization velocity, the solid particle separated Advantages - FCC riser
and results in expansion of packed bed - temperature control and heat recovery is - Spherizone technology
easy to achieve - Sasol FT process to produce syncrude
Bubbling fluidization: further increase in gas velocity leads to - flexibility in changing feed rate and
formation of gas bubbles. The bed moves in agitated fashion residence time
- easy to unload catalysts
Slugging fluidization: individual bubbles become more frequent Shortcomings
and bed move agitated - catalyst removal is required. Usually done
by filtration
Lean phase fluidization with pneumatic transport (SSTR): gas - higher consumption of catalyst than
velocity too high and solid particle well apart and are merely packed bed
carried along by the gas stream - difficult to scale up compared to packed
Advantages bed reactor due to complicated
- uniform temperature gradient due to high mass and heat transfer hydrodynamic flow profile
- can use small sizes of catalyst because good for fast reaction Applications
when pore and film diffusion may influence the rate - bubble column reactor
- can be unloaded and regenerated easily because it is good for - mechanically agitated slurry reactor
system with catalyst that are deactivated easily - venturi/jet loop reactor
Shortcomings - tubular loop reactor
-flow is complex with considerable bypassing, hence it requires
much more catalyst for high conversion and bigger reactor volume
-high pumping requirement due to considerable pressure drop
- erosion of internal components results in wear of reactor vessel
Applications
- Fluidized catalytic cracking (FCC) (to convert high BP and MW
fraction crude oil to more valuable gasoline and gases)
- Unipol process (convert gaseous ethylene and comonomer to
polyethylene)
- gas-solid vortex reactor

OTHER REACTORS
- Catalytic membrane reactor - space propulsion thruster
- reactive distillation - personal propulsion thruster
- monolithic reactor
- spinning basket reactor
- wire gauze reactor
PSM CHAPTER 1: INTRODUCTION TO PROCESS SAFETY
 IMPORTANCE OF SAFETY

FundamentalUnsafe
typesacts Unsafe conditions
- unauthorized use or operation of - lack of adequate guards or safety
equipment of accident
Important cause
definitions devices
- operating or working at unsafe - lack of adequate warning systems
speed (jumping steps or taking - fire and explosion hazards
shortcut) - accident: an unexpected, unforeseen and unintended - poorevent that cause injury,
housekeeping, especially
- using defective tools or loss or damage slippery surfaces
equipment - type of losses: loss of time, production/sale, lives, other defective
- using indirect hidden loss
tools or equipment
- safety or loss prevention is the prevention of accidents using appropriate
technologies to identify the before and accident occurs
- Hazard: a chemical or physical condition that has the potential to cause
damage to people, property or environment
- risk: a measure of human injury, environmental damage or economic loss in
terms of both the incident likelihood and the magnitude
 SAFETY of the loss of injury
PROGRAM
1. SYSTEM
-to record what need to be done to have
an outstanding safety program

2. ATTITUDE
-willingness to do some of the thankless
 ACCIDENT AND LOSS STATISTICS work that is required for success
-important to determine whether a process is safe of whether a safety procedure is working effectively 3. FUNDAMENTALS
-3 systems to measure accident and loss performance are: i) OSHA incident rate -understand the fundamentals of
ii) Fatal accident rate (FAR) chemical process safety in term of
iii) Fatality rate, or deaths per person per year design, construction and operation.

4. EXPERIENCE
i) OSHA (occupational safety &health act) incident rate -learn for the past experience or history
- OSHA incidence rate is based on cases per 100 worker years 5. TIME
- A worker year is assumed to contain 2000 hours -time to study, works, record result,
- therefore, OSHA incident rate is based on 200,000 hrs of worker exposed to hazard share experience and train

6. YOU
-take responsibly to contribute to safety
program
 40 hrs 50 weeks hrs
Worker year = × =2000
weeks yr yr
(assume works 8hr a day, and 5dy per week)

number of injuries∧ilness ×200,000

OSHA (based on injuries∧illness)=
total hours worked by all employees during period covered

number of lost workdays ×200,000

OSHA (based on lost workdays)=
total hours worked by all employees during period covered

ii) Fatal accident rate (FAR)

- based on 1000 employees working their entire lifetime Both OSHA and Far depend on the
- employees are assumed to work a total of 50 years number of exposed hours
- thus, the FAR is based on 108 working hours.
-FAR can converted to fatality rate
(vice versa) if the number of
number of fatalities ×108
FAR= exposed hours is known
total hours worked by all employees during period covered
-OSHA cannot be converted to
FAR or fatality rate
iii) Fatality rate, or deaths per person per year
- represent death per person per year
- independent of the number of hours actually work and reports only the number of fatalities
expected per person per year
- useful in calculate the population where the number exposed hour is poorly defined

number of fatalities per year

fatality rate=
total number of people ∈applicable population

 ACCIDENT RISK
- risk is the product of probability of the occurrence of an accident and severity of the accident
- risk cannot be eliminated entirely
-therefore, necessary to decide if the risk is in “acceptable level” at some point in the design stage
- engineers should try to minimise risks within the economic constraints of the process
 INHERENT SAFETY
- Relies on the chemistry and physics to prevent accidents rather than on control system, interlock, redundancy and special operating procedures to prevent
accidents
- the safety of the process relies on multiple layer of protection
1st layer: process design feature
2nd layer: control systems, interlocks, safety shutdown systems, protective systems, alarms and emergency response plants.
-inherent safety is especially direct toward process design features
- the best approach to prevent accident is to add process design features to prevent hazardous conditions
- the most significant effect to increase inherent safety of a process or plant is in the initial stage of process development
- four words are recommended to describe inherent safety
i) minimize (intensification)
 reducing the hazards by using smaller qualities of hazarding substances in reactor,
distillation column, storage vessel, pipeline
 hazardous material should produce and consumed in situ, to minimize the storage and transportation of hazardous raw materials
 vapours released from spills can be minimized by designing dikes to reduce accumulation of flammable and toxic materials around leaking tanks
 smaller tanks can be reducing the release of hazards materials
ii) substitute (substitution)
 safer materials should be used top replace the hazardous one by using alternative chemistry that allow the use of less hazardous materials or less
severe processing conditions

iii) moderate (attenuation and limitation of effects)

 using hazardous materials under less hazardous condition such as diluting to a lower vapour pressure, refrigerating to lower the vapour pressure,
using larger particle size solids, processing under less severe temperature and pressure
iv) simplify (simplification and error tolerance)
 simpler plant provides fewer opportunities for error because contain less equipment
 complexity of plant is caused by the need to add equipment and automation to control the hazards
 PSM CHAPTER 2: TOXICOLOGY Animal toxins Heavy metals
 DEFINITIONS
-Toxicology: Qualitative and quantitative study of the adverse effect of toxicants Dioxin/Furans
on biological organism
Classification of
-Toxicants: Physical (dust, heat, noise, asbestos fibres)
Toxic Agents
Chemical agents (poisons)
Biological (pathogens) Plant toxins
-Toxicity: of the chemical or physical agent is a property of the agent describing its Solvents and Vapour
effect on biological organisms.
pesticides Radiation and
Analytical radioactive materials
Environmental toxicology
Sub-disciplines of toxicology
- Contaminants of food,
water soil toxicology
Forensic toxicology
Mechanistic
Occupational (industrial)
Toxicology
toxicology
Regulatory Clinical Toxicology
- expose to chemicals in
toxicology Description
workplace
Food toxicology Toxicology

 STUDY OF TOXICOLOGY
EN (ENTRY) EF (EFFECT) EL (ELIMINATE) AV (AVOID)
- Ingestion (through mouth to stomach, Irreversible effects - excretion
2nd lowest in bloodstream concentration) - carcinogen  causes cancer - detoxification Method for control
- Inhalation (through mouth/nose, 2nd - Mutagen causes chromosome - storage
 highest in bloodstream concentration) damage ingestion  enforcement of rules on
- injection (through needle into skin, - Reproductive hazard  damage to eating, drinking and smoking
highest in bloodstream concentration) reproductive system inhalation  ventilation, respirators,
- dermal absorption (through skin - Teratogen  causes birth defects hoods and other protection equipment
membrane, lowest in bloodstream injection  proper protective clothing
concentration) dermal adsorption  proper protective
clothing

 DOSE VS RESPONDS

 DOSE LIMIT VALUES

• ED – effective dose. the response to the chemical or agent is minor and reversible.
Can also be known as the amount of a drug, that is sufficient to achieve the desired
clinical improvement.
• TDf – Toxic dose. Undesirable response that is not lethal but is irreversible.
• LDf – Lethal dose. Dose that results in lethality.
• LD50 = Dose that results in 50% lethality.
• TD10 = Dose that results in 10% of toxicity.

 MODEL FOR DOSE AND RESPONSE CURVE

For computational purpose, the “Response vs. dose” curve is not convenient
P=50 1+
[ Y −5
|Y −5|
erf
|Y −5|
( √2 )] where erf = error function, Y= probit variable, P= probability

Y =k 1 +k 2 ln V where V, k1, k2 can be obtained from table

 THRESHOLD LIMIT VALUES (TLV)

converting from mg/m3 to ppm
 22.4 T
C ppm= ( )( P1 )mg/ m
M 273
3
 PSM CHAPTER 3: INDUSTRIAL HYGIENE
 DEFINITION
-Definition 1: IOHA  Occupational hygiene is the discipline of anticipating, recognizing, evaluating and controlling health hazards in the working
environment with the objective of protecting worker health and well-being and safeguarding the community at large.
-Definition 2: AIHA  That science and art devoted to the anticipation, recognition, evaluation and control of those environmental factors and stresses arising
in or from the workplace, which may cause sickness, impaired heath and well-being, or significant discomfort among workers or among citizens of the
community
Government regulation
- protecting people and environment
Typical Industrial Hygiene Practices Anticipation of chemical hazards
-applicable government agency develops and
- Monitoring toxic airborne vapor concentration - OSHA has established permissible exposure limits
proposes a regulation: EPA, OSHA, DHS
- reducing toxic airborne vapor through ventilations (they are defined in time weighted average, TWA for
-selecting proper personal protection equipment to HYGIENE most working conditions, STEL and C)
prevent exposure - ACGIH has established threshold limit values, TLV
-developing procedures for handling hazardous
chemical/materials
-work site analysis: housekeeping, lighting, floors and GOAL OF INDUSTRIAL HYGIENE
drainage
Anticipation (expectation of the presence of workplace hazards and worker - most difficult
exposure) -essential for estimation of exposure and response to one or more hazards
-estimate level of risk, safety professional would need to know
Identification (determine the presence of exposure) - Involved a detail study of chemical process, operating condition and
operating procedures
- required information included: process design description, operating
instructions, safety review, equipment description, information from
chemical supplies, information from operating personnel
-one of the most important reference is MSDS
Evaluation (determine the magnitude of exposure) - Determine the extent and degree of employee exposure to toxicant/physical
hazards in workplace environment
- evaluating exposure to volatile toxicants by monitoring
- evaluating worker exposure to dust
- evaluating worker exposure to noise
- evaluating worker exposure to toxic vapours
- estimating the vaporisation rate of liquid

Exposure to volatile toxicants

 Single volatile toxicants Multiple volatile toxicants

TWA Concentration (TLV-TWA)mix

Alternative 1: If the summation of the equation >1, then

TWA=
∑ Ci T i Alternative 1:(TLV −TWA)mix =∑
n
Ci
the worker is overexposed. ∑ Ti i=1 (TLV −TWA)i
Alternative 2: If the summation of the equation > n
(TLV −TWA)mix , then the worker is overexposed. ∑ Ci
i=1
Alternative 2: (TLV −TWA)mix = n
i C
∑ ( TLV −TWA)
i=1 i

****Alternative 1 and 2 can be used to evaluate Worker Exposure to Dusts

and Noise
the Evaluating Worker Exposure to Toxic Vapor and evaluating the
Vaporization Rate Of Liquid can be calculated using following formula:

Qm RgT KA Psat
concentration of volatile component , C ppm= ×106 = × 106
k Q v PM k Qv P

MKA Psat
vaporisation/evaporation rate of liquid , Q m=
Rg T L
1 /3
M0
K= K 0 ( )
M
where Qv =ventilation rate
k = mixing factor, 0.1-0.5; k =1.0 =perfect mixing

Control (application of applied technology to reduce exposure to acceptable - Environmental controls: reduces exposed by reducing the concentration of
level) toxicants in the workplace environment which includes enclosure, installation
of ventilation, wet method and good housekeeping
- Personal protection: prevents or reduces exposure by providing a barrier
between worker and the workplace environment
PSM CHAPTER 4: CHEMICAL REACTION SAFETY
 CLASSIFICATION  to know the potential for a chemical to cause harm, hence a classification of chemical hazards is the way to identifies the harm of
the chemical e.g., flammable chemical, reactive chemical, health hazards, fire hazard, toxic chemicals, corrosive chemical

Factors that create reactivity hazards:

 LABELLING -intentional chemistry
****MORE LABELLING REFER TO NOTE -physical processing
- hazardous substance storage
- processes that involve combustion
- heat generating process
- the presence of (spontaneously combustible
chemical, peroxide-forming chemicals, water-
reactive chemicals, oxidizing chemicals, self-
reactive chemicals, materials that are incompatible

 INVENTORY OF CHEMICALS
-An itemized catalog or list of tangible goods or property or the intangible attributes or qualities
-A master inventory of chemicals in use must be established at workplace
-the inventory should include every chemical used, its physical state and the estimated quantity used per month
-this inventory process can only be accomplished by inspecting every work station, raw materials depot and storage area.
-method used for the transport, handling storage and disposal of chemical should also be noted.
 CHRA
OBJECTIVE CHRA METHODOLOGY
WHY DO CHRA/ BENEFIT OF CHRA HAZARD ON CHRA DEFINATION ASSESSMENT

Hazard Identification  Risk Assessment  Risk Control

  PRESSURE EFFECT
-Investigation on pipe and vessel
-Pressure necessary to produce a specific stress in a vessel depends on:
- thickness of the vessel
- vessel diameter
- mechanical properties of the vessel wall
For cylindrical vessel For cylindrical vessel
SM t v 2 SM t v
p= (p<0.3885Sm) p= (p<0.665Sm)
r +0.6 t v r +0.2 t v
2 2
tv tv

p=
( )
S M +1 −S M
r
(p>0.3885Sm) p=
2 SM ( )r
+1 −2 S M
2 2
tv tv
( )
r
+1 + 1 ( )r
+1 +2

(p>0.665Sm)

 PRESSURE PILING
 CCUPATIONAL SAFETY MANAGEMENT -Describe phenomena related to combustion of gases in a tube or long vessel
where the pressure will increase in front of the flame front as the flame
travels through the network.
-As the flame front propagates along the tube, the unburned gases ahead of
the front are compressed, and hence heated.
-Where multiple vessels are connected by piping, ignition of gases in one
vessel and pressure piling may result in a deflagration to detonation
transition and very large explosion pressure.
Pressure piling for deflagration
P2
= 8 (for hydrocarbon-air mixture)
P1
P2
= 16 (for hydrocarbon-oxygen mixture)
P1
 -Ignition sources are so plentiful that it is not a reliable control method.
-Robust Control: Prevent existence of flammable mixtures.
-Fire=release energy slowly
-Explosion=release energy rapidly
-fire and explosion may trigger each other
PSM CHAPTER
-Flammability limits: Vapor-air mixtures will
5: FIRE AND
ignite and burn only over
EXPLOSION
a well-specified range
 THE FIRE TRIANGLE of compositions.
-The mixture will not burn if the composition is
lower than the lower flammable limit (LFL) or
higher than the upper flammable limit (UFL)
-Too little fuel (lean mixture) not enough fuel to
 Both are for at 25℃
 THE FLAMMABLE DIAGRAM

Both are for at Other temperature

Estimation of overpressure
Two types of explosion: Deflagration and Detonation.
-Overpressure can be estimated using an equivalent mass of TNT,
-Deflagration: An explosion in which
mTNT. the reaction front moves at speed less
than the speed of sound in the unreacted medium.
-Detonation: An explosion in which the reaction front moves at speed greater Z 2
than the speed of sound in the unreacted medium
-Explosions result in a blast or pressure
r
- Z e= wave
1 /3 moving Pout
s =
PO
from= the explosion
[ ( )]
1616 1+ e
4.5
m TNT Pa Ze 2 Ze 2 Ze 2
centre at the speed of sound.
√ (1+
-Blast wave: A pressure wave propagating in air because the pressure0.048
followed by a strong wind.
)√ ( )√ ( )
wave is
1+
0.32
1+
1.35

❑ nm ∆ H c
–A shock wave results if the pressure
-m TNTfront
= has ❑ an abrupt pressure change.
-The maximum ambient pressure is called peak E TNT overpressure.
Designs to Prevents Fires and Explosions
-The possibility of a confined explosion can be considerably reduced by
operating outside flammability limits; this can be performed by the appropriate
use of an inert gas
Inerting
-A process of adding an inert gas to a combustible mixture to reduce the
concentration of oxygen below the limiting oxygen concentration (LOC)
-Inert gas usually nitrogen or carbon dioxide but sometimes steam
-Inerting begins with an initial purge of the vessel with inert gas to bring the
oxygen concentration down to safe concentrations
-For many gases the LOC is approximately 10%, and for many dusts it is
approximately 8%
-A commonly used control point is 4% below the LOC, that is, 6% oxygen if the