Process Development

CHEE 2404
A Ghanem
 Process Development

• Development of new technologies and products

is a Research and Development (R&D) activity
• Goal: produce the desired product
– In time
– At planned rates
– At projected manufacturing cost
– At desired quality standards

• Cost and planning are continually monitored

from lab phase to production
 Product type and raw materials
• Type of product determines the way
Process Development is conducted.
• Base chemicals (commodities) and
intermediates can be dictated by the
type of raw materials available.
• Base chemicals have a wide range of
uses and a long lifetime.
• Benefit to lowering the cost of
production. Process improvement.
• Consumer products on the other
hand, will be quickly replaced
(shorter lifetime). Product
improvement.
 Base chemicals
• The technologies for the production of base chemicals
and intermediates are well established.
• Development activities usually result in minor process
improvements (example a new catalyst or a more energy
efficient furnace)
• Still can have a large impact on overall costs due to the
large volumes involved (example, saving dollars per
tonne of acetic acid can have a large impact when you
produce 500,000 t/a).
• Major new advances in processes are still worth
pursuing
• More general drive is sustainability and process
intensification
 Consumer Products
• In specialty chemicals, drive is toward modified or new
products
• Motivated by market demands rather than cost savings
• Some market demands can include new products,
product quality or environmental concerns.
• Some examples are environmentally friendly paints,
varied detergents, wood composites used in building
materials, new drugs, etc.
• More effort is required in determining the chemical route
of manufacturing. For example, a when a new drug is
approved the manufacturing route must also be
approved.
Bulk vs Specialty Chemicals
 Process Development
• Continuous interaction between experimentation and
economics.
• Input: chemical reaction in the lab
• Outcome: production plant

• Development of a process to take the chemical reaction in

the lab up to a large plant scale in an economic way.
• Enlargement of equipment in small steps? Empirical
method, and practical for some applications but not
generally for continuous process.
Scale Up
• Scale up in small steps is expensive especially
for larger continuous production plants.
• Large safety margins are used.
• Time scale shown is very long (8 years...need to
reduce time to process development) due to
time associated with design/construction and
operation of small steps.
• Predictive models: Process steps described in a
Mathematical model with predictive value
• Predictive models are used to scale up
equipment and processes from laboratory data
or pilot plant to eliminate steps and save time.
• Exploratory phase: the reaction provides
satisfactory yields.
• Based on lab data and literature data, the
process concept is put together.
• Individual steps are developed and tested on a
lab scale (the reactor, does the required
separation work?)
• A process flow sheet is drawn.
• A small scale plant is designed (mini-plant) to
evaluate performance of the entire process.
• A pilot plant may be designed and built for
further testing.
• At each stage, evaluation occurs. Continue,
stop, or go back to an earlier stage?
• Decisions are based on technical, cost and
market considerations.
Cyclic Nature of Modern Process Development
 Breakdown of Steps

• Exploratory Phase
– Discovery of a new product, a new chemical synthesis
route, or an improvement to a process
– Focus on chemical reaction
– Obtain information:
• what reactions take place
• thermodynamics and kinetics of the reaction
• selectivity and conversion rates and their
dependence on process parameters
• Catalyst and catalyst deactivation rate
 Breakdown of Steps
• Preliminary Flowsheet
– Determine the availability and quality of raw materials
(first design step would be compare raw material
costs with product value)
– Draw up preliminary flowsheets and alternatives
– Typically underdefined, so we must make
assumptions.
– What units should be used?
– How will the units be connected?
– What T, P and flowrates will be required?
– Difficult b/c there are many ways we can accomplish
the goal, problem is open ended.
• Process requirements:
– Lowest cost
– Satisfies environmental constraints
– Easy to start up and operate
• We can eliminate alternatives based on the
above considerations
• Make the optimal choice based on knowledge,
experience and tools such as process simulation
 Input Information
• The reactions and reaction conditions
• Desired production rate
• Desired product purity ($ vs. purity)
• Raw materials (also need $ vs. purity info here)
• Information on rate of reaction, catalyst deactivation
• Processing constraints? (ex. explosion limits, conditions
that cause polymerization, etc.)
• Plant and Site data
• Physical properties of all components
• Information on safety, toxicity, environmental impact of
materials involved in the process.
• Cost data for byproducts, equipment and utilities.
 1. Reactor system…2. Separations

• Reactor System
– First step
– Includes reactor, feed, product gas and liquid recycle
streams.
– Influences the yields, product distribution and
separations.
– example: coal gasification, the amount of H2 and CO2
formed are very different for a moving bed, fluidized
bed, and entrained flow reactor.
– Determine T and P, type of catalyst, phases of
reactant and products
 Reaction Information

1. Stoichiometry of reactions taking place

2. Range of T and P for the reactions
3. Phases of the reactions
4. Product distribution vs. conversion
5. Conversion vs. residence time
6. Information on the catalyst

Often available from the literature

Identify any side reactions that may take place
 Decision 1: Batch vs. Continuous?
• Production rates
– Capacity ≥ 10x106 lb/year, usually continuous
– Capacity≤ 1 x 106 lb/year usually batch.
– Multiple products in same equipment?
• Market Forces
– Seasonal products (fertilizer)
– Products with a short lifetime
• Operational Problems
– Reaction is very slow
– Slurry pumping, materials handling considerations.
– Rapidly fouling materials
 Conceptual Design

• Continuous Process:
– Select the units needed
– Choose the interconnections between these units.
– Identify process alternatives that should be
considered.
– List the dominant design variables.
– Estimate optimum processing conditions.
– Determine the best processing option
 Conceptual Design

• Batch process (in addition to previous decisions)

– Which units in the flowsheet should be batch and
which should be continuous?
– Which steps can be carried out in a single vessel vs.
using a special separate vessel for each step?
– Is it advantageous to use parallel batch units? Think
about scheduling.
– Intermediate storage requirements?
 Decision 2: inputs and outputs

• Should you purify the feed streams before they

enter the process?
• Should you remove or recycle a by product?
• Should you use a gas recycle or purge stream?
• Should you recycle unreacted reactants?
• How many product streams will there be?
 Decision 3: Separations
– Reaction product contains multiple components, you
must decide how they will be separated and at what
conditions.
– Look at the components and how they differ (ie boiling
point, solubility)
– Identify possible unit operations (ie. Distillation,
absorption, adsorption, solvent extraction, etc.)
– If reactor effluent is a liquid, use liquid separation
system
• distillation
• liquid extraction, etc.
• Avoid gas absorbers, gas adsorbers.
– If reactor effluent is a 2 phase mixture, send liquid to
a liquid system, cool the vapour and send to vapour
recovery
– Condenser
– Absorption
– Adsorption
– membrane separations).
– If either stream has reactants, recycle these.
– Reactor effluent all vapour – cool to attempt to
condense liquid. Follow up by sending vapour to
vapour recovery, liquid to liquid recovery.
Heuristic rules for distillation sequence
• Remove corrosive or hazardous components as soon as
possible
• Remove reactive components or monomers as soon as
possible
• Remove products as distillates
• Remove recycles as distillates, particularly if they are
recycled to a fixed bed reactor
• Remove most plentiful first
• Remove Lightest first
• High recovery separation last
• Difficult separation last
Example: Production of cyclohexanone
• Product mixture:
– cyclohexane 94%
–
Boiling point
Light products 0.5%
– Cyclohexanone 3.0%
– Cyclohexanol 1.5%
– Heavy products 1.0%
All products are similar in terms of corrosiveness, hazard and
reactivity.
1) Remove cyclohexane first (most plentiful and lightest)
2) Separating cyclohexanone and cyclohexanol is the most
difficult, so do this last.
3) Remove heavy or light components next? Heavy since they
are more plentiful.
4) Remove light products
• Draw the flowsheet of selected operations
• Sizing of unit operations is done based on
available information at that time (this is
preliminary as not all data is available yet, an
iterative process).
• Develop and test the individual steps.
• Laboratory tests conducted on mixtures
prepared from pure materials, typically short
duration, may not show some problems.
• Pilot plants are the next step
 Pilot Plants
• An experimental system that represents the part it
corresponds to in an industrial unit.
• Can range in size from lab scale (mini plant) to
commercial unit (demonstration plant).
• Used to :
– generate more product to develop a market
– confirm feasibility of the process
– check design calculations
– solve scaleup problems on novel processes
– gain operational know-how
– Determine long term effects of operation
• Typically run to 10% of the commercial plant cost.
 Mini-plant
• To demonstrate process feasibility or generate design
data for a process, then a mini plant may be more
appropriate than a pilot plant.
• Includes all recycle streams and can be extrapolated
reliably
• Uses same components as the lab testing (ie pumps,
etc.), which is often standardized and can be used in
many other mini plants
• Operated continuously for weeks or months so some
automation is required.
• Is used in combination with process modeling and
simulation of the industrial scale process.
• Typically produces 0.1-1 kg product per hour.
 Relationships of scale

Production rate Scale Up Factor

(kg/h)
Industrial 1000-10,000 -
Plant
Pilot Plant 10-100 10-1000
Miniplant 0.1-1 1000-100,000
 Miniplants
• Can help to speed up process development and
at a lower cost.
• Useful to test catalyst stability under practical
conditions.
• Incorporate recycle streams to detect buildup
and effect of impurities.
• Some unit operations not easily scaled from
miniplant data (extraction, crystallization,
fluidized beds) due to flow characteristics.
• See fig 13.3 for some scaleup values
Requirement for Pilot Plant Testing
 Reactor Scale Up
• Homogeneous Reactors (single fluid phase)
• Easier to scale up than heterogeneous
• Batch or semi-batch reactor
– Main issue is heat removal in highly exothermic reactions
• Continuous tubular reactor
– Main issue is heat transfer and T profile in the reactor, kinetic
modeling of reactions is used to relate the reaction to
temperature
• Continuous stirred tank reactor
– Scale up from batch reactor kinetic data
 Heterogeneous Reactors
• Examples include steam reforming, ammonia
synthesis, hydrotreating.
• Main issues are T control, P drop and Catalyst
deactivation
• Temperature control
– In endothermic reactions the T drop may be severe
resulting in an excessively long reactor
– Reaction mixture must be heated rapidly to keep the
reaction rate at a high enough level
– One way of doing this is to conduct reaction in tubes
in a furnace (steam reforming)
• Temperature control
– Exothermic reactions need to be cooled
– This can be done by external heat exchangers,
injection of cold feed gas.
• Pressure Drop
– Pressure drop across a catalyst bed must be limited
– Reduce the bed height, use larger particles, apply
axial flow or structure the reactor.
• Catalyst deactivation
– Design strategies depend on the mechanism of
catalyst deactivation
• Catalyst deactivation
– For example, if the catalyst is deactivated by coke
deposits, regeneration occurs by burning off coke.
This can be done in a fluid bed reactor.
– Impurities may build up in the system that are
undetected at lab scale (low concentration), that may
affect the catalyst if they are recycled. Larger scale
reactions are needed to detect these so processes
can be established to deal with them.
– Install pretreatment units, purge some of the recycle
stream.
• Hyrodynamics
– Fluid distribution in a heterogeneous reactor may
change as you make a reactor larger.
– Gas-liquid, solid-liquid contacting
– Parameters include diameter and height, residence
time, catalyst particle size
 Safety and Loss Prevention
• Chemical plants involve process, storage and transport
of hazardous materials.
• Increasing plant size increases risks
• Plants are often located close to dense populations.
• Loss prevention: identify the hazards of a chemical
process plant and eliminate them.
• Major hazards:
– Explosion
– Fire
– Release of toxic substance
 Flammability
• Fires and explosions
• Fuel, oxidizer and ignition source
 Toxicity

“The dose makes the poison”

• Hazard depends on the inherent toxicity

• Frequency and duration of exposure
• Acute vs. chronic effects
• LD50: lethal dose that kills 50% of test animals
• TLV: threshold limit value, conc of exposure for 8 hours
a day, 5 days a week, without harm.
• Strategies: substitution, containment, ventilation,
disposal provisions, Good manufacturing practices
(GMP)
 Reactivity Hazards

• Exothermic runaway reactions

• Reactions can occur anywhere
• Unused Catalysts may mediate undesired
reactions
• Have good knowledge of reaction chemistry and
reaction enthalpies
• Use of nitrogen blanket to keep systems inert
 Process Evaluation

Evaluate at each stage of development

• Is the process technically feasible?
– This is determined at the laboratory, flowsheet design,
and pilot plant level
• Is it economically attractive?
• How big is the risk (economically, technically)?