Examples of Innovations in
Distillation Technology
J Chem Technol Biotechnol 2014; 89: 479–498
45-90 = refinery and petrochemicals
91-127 = green chemistry
127 to end = PI
Dividing Wall Column
Dividing Wall Column (DWC), TDWC & BDWC
PROCESS DEVELOPMENT AND ENGINEERING
Course Content
Development of a preliminary process system: Modular approach 2h
Multiple process synthesis, selection of process, basic economic evaluation 2h
Sequencing of operations and integration in processes 2h
Batch vs continuous vs semi-batch processes – Scale up 3h
Process engineering aspects of low and medium volume chemicals including process development 3h
Concept of dedicated and multiproduct plant facilities, pilot plant, mini plants 3h
Development and evaluation of alternative flow sheets 3h
Scale up aspects; identification of controlling steps of process 3h
Green engineering principles 6h
Utilisation of energy; cost of utilities, heat exchange networks 3h
Process intensification 3h
Preparation of conceptual process and instrumentation diagrams 3h
Preparation of process specifications for typical equipment 3h
Safety and Risk of chemical processes 3h
Learn from mistakes 3h
Outcome: Design a plant to manufacture ……..
Design considerations:
Project summary:
Product properties & uses Useful features:
Product & its uses Market analysis
Indian scenario Volume
Technical knowhow
Sales turnover Process comparison Price
Feedstock requirement Process selection Lifecycle
Process schematic Molecules
Cost of production
Site selection Applications
Financial information
Kinetics & thermodynamics
Process description Synthesis
Material & energy balances
Project site & supplies Equipment sizing & design Catalysis
Material balances Instrumentation & process control Processing
Safety, Health & Environment HAZOP, LOPA By-products (kg/kg)
Safety, Health & Environment Waste per kg product
Utilities
Site & plant layout
Conclusions Project economics
Design a plant to manufacture ……..
Learn these lessons:
Avoid these pitfalls:
Calculate the plant capacity
Choosing the wrong capacity
Batch or continuous
Selecting improper raw material
Check sustainability
Using incomplete literature search
Manufacture smartly
Choosing the wrong process
Check if process can be intensified
Selecting improper plant site
Mitigate pollution
Neglecting kinetics & thermodynamics
Choose proper equipment
Making incomplete PFD
Think about plant utilities
Using improper assumptions
Troubleshoot problems
Using improper physico-chemical data
Conduct process inspection
Using erratic energy balances
Take appropriate measurements
Selecting wrong reactor type
Monitor equipment to prevent failure
Not considering process intensification
Prevent or minimize corrosion
Underdesign or overdesign equipment
Save energy; Perform energy assessment
Wrong sizing
Optimize energy use in distillation
Neglecting mechanical design
Think safety first; Protect your process
Neglecting process control & instrumentation
Bring safety in design
Costing with improper data/assumptions
Streamline process hazard analysis
Misrepresenting financial analysis
Integrate HSE into project
Using wrong procedures for scale-up
Scale-up
Learn from Examples – No. 1: Ammonia Production
Early cyanamide process
Alternative process
The early works of Haber and Nernst
The influence of T and P on
Low per pass conversion and Haber’s recycle idea equilibrium NH3 content
BASF’s first commercial process (1913) for 30 m.t./day
Ammonia Production
BASF’s first commercial ammonia plant
Worldwide ammonia production has steadily increased
Modern Production Processes - KBR’s first single-train, large-capacity ammonia plant
Plant designs in the 21st century - KBR’s modern ammonia plant with proprietary purifier design
Haldor-Topsoe’s ammonia plant design with proprietary side-fired reformer
ThyssenKrupp’s dual-pressure synthesis loop design with once-through reactor
Linde ammonia concept with PSA and ASU
Other technologies - Ammonia from coal in China
Evolution of Ammonia Production
Ammonia process technology has drastically improved during the past sixty years
Plant layout has evolved from multi-train to single-train designs
Synthesis gas preparation in front end of plant increased from atmospheric pressure to 30-50 barg pressure
Capacities increased from 100 to 3300 m.t./day in a single train
Energy efficiency has increased (consumption increased from >60 MJ/m.t. of ammonia in coke-based plants to
40-50 MJ/m.t. in natural-gas based plants to 30-40 MJ/m.t. in the first single-train plants). Modern plants recover
heat by producing steam at 125 barg in syngas preparation section and synthesis loop
In terms of process equipment, there is a shift from reciprocating to centrifugal compressors
Internal heat exchanger is implemented in synthesis converter to increase conversion to ammonia
Hydrogen is recovered from purge gas in PSA to increase production or reduce plant energy consumption
Designs with hot feed gas desulfurization systems are implemented
Catalysts for reforming, shift, methanation and ammonia synthesis have improved
Distributed control systems (DCS)and safety instrumented systems (SIS) are used to improve process control and
safety
HAZOP studies and LOPAs are performed before any process goes online
Such improvements in technology and safety have made ammonia industry productive and safe
Learn from Examples – No. 2: A Technical History of Methanol Production
Introduction
The first drops
The German effort
Early catalysts
Early processes
Catalyst developments
The British intervention
Methanol converters
Capacity expansion
Synthetic fuels
Autothermal reforming
Modern catalysts
China – the coal story
Thermodynamics of Methanol Production
Thermodynamic equilibrium methanol concentration
(feed – 15% CO, 8% CO2, 74% H2, 3% CH4)
Effect of pressure on thermodynamic equilibrium of methanol production at 300 oC
Pressurized Methanol Synthesis Loop
Methanol Converters
Reaction path in a quench converter Reaction path in a water-cooled converter
ICI Low Pressure Process
Added global methanol capacity by year
Learn from Examples – No. 3: Production of Nitric Acid
The NH3 into NO conversion efficiency
increases with decreasing pressure, whereas
the conversion of NO into NO2 and the
subsequent absorption is favoured by high
pressures.
Thus, modern nitric acid plants are dual
pressure processes, that is, the product gas
of ammonia oxidation (at 6 bar) is
compressed to 12 bar and then fed to the
absorption tower for NO oxidation and for
NO2 absorption.
Single Pressure Nitric Acid Plant (High Pressure)
Dual Pressure Nitric Acid Plant
Plant Configurations for the Production of 1 t Nitric Acid
Learn from Examples – No. 4: Production of Acetic Acid
Global production capacities Applications of acetic acid
Acetic Acid Processes
Monsanto Process for Production of Acetic Acid
Learn from Examples – No. 5: Acrylamide from Acrylonitrile
Innovations in Refining and
Petrochemicals
PROCESSES, CATALYSTS, STRATEGIES, PRODUCTS, REACTOR
CONFIGURATIONS AND APPLICATIONS
OIL REFINERY – A GLANCE
FLUID CATALYTIC CRACKING (FCC)
FCC CATALYSTS
FCC CATALYSTS
FCC CATALYST INGREDIENTS
USE OF ADDITIVES
ZSM-5 ADDITIVE
MAIN CATALYTIC CRACKING REACTIONS
GROWTH OF FCC TECHNOLOGY
IOC INDMAX TECHNOLOGY – RESID TO OLEFINS
CATALYTIC REFORMING - CONVENTIONAL UNIT (FIXED-BED)
TEMPERATURE AND COMPOSITION IN REACTORS
DUALFORMING
CONTINUOUS CATALYTIC REGENERATIVE REFORMING
INDIA - PRODUCT DEMAND AND REFINING CAPACITY
STRATEGIES TO MAKE PROFIT
REFINERY – PETROCHEMICALS INTEGRATION
REFINERY – PETROCHEMICALS INTEGRATION
PETROCHEMICAL PROCESSES WITHIN A REFINERY
PETROCHEMICALS – PRODUCT SLATE
CATALYTIC ROUTES FOR AROMATICS
REFINERY STREAMS FOR CHEMICALS/PETROCHEMICALS
VALUE CHAIN FROM REFINERY STREAMS
VALUE CHAIN FROM REFINERY STREAMS
AROMATIC NAPHTHA-BASED CHEMICALS/PETROCHEMICALS
AROMATIC NAPHTHA-BASED CHEMICALS/PETROCHEMICALS
ETHYLENE-BASED CHEMICALS/PETROCHEMICALS
PROPYLENE-BASED CHEMICALS/PETROCHEMICALS
PROPYLENE-BASED CHEMICALS/PETROCHEMICALS
C4-BASED CHEMICALS/PETROCHEMICALS
PE – EVOLUTION TO REVOLUTION THROUGH CATALYST
PP – CATALYST DEVELOPMENT
IMPACT OF CATALYST DEVELOPMENT ON POLYOLEFIN MANUFACTURE
IMPACT OF CATALYST DEVELOPMENT ON POLYOLEFIN MANUFACTURE
CRITICAL FACTORS FOR SUCCESSFUL CATALYST PERFORMANCE
FAMILIES OF POLYOLEFIN CATALYSTS
POLYOLEFIN CATALYST TECHNOLOGY LIFECYCLE
POLYOLEFIN CATALYSTS – MAIN CHARACTERISTICS
COMMERCIAL PE CATALYSTS
PP ZIEGLER NATTA CATALYSTS
PP ZN CATALYSTS - GENERATIONS
COMMERCIAL PP ZN CATALYSTS
POLYOLEFIN MANUFACTURING PROCESS
SUMMARY OF SEVERAL REACTOR CONFIGURATIONS
Green Chemistry and
Innovation
Designing for a green chemistry future
Zimmerman et al., Science 367, 397–400 (2020)
Characteristics of today’s and tomorrow’s chemical sectors.
Zimmerman et al., Science 367, 397–400 (2020)
Decision tree for chemical design.
Zimmerman et al., Science 367, 397–400 (2020)
Zimmerman et al., Science 367, 397–400 (2020)
Green Chemistry
Circular Economy via Green Chemistry
Benefits of Green Chemistry
Timeline of Key Concepts in Green Metrics
Green Chemistry Metrics
Green Chemistry Examples
Green Solvents
Alternate Feedstock
Alternate Feedstock
Alternate Feedstock
Waste Valorisation
Waste Valorisation
Waste Valorisation
Waste Recycling
Green Alternative Products
Catalysis for Sustainability
Catalysis for Sustainability
Catalysis for Sustainability
Innovative Pathways
Innovative Pathways
Industrial Examples
Green Route for DMC Synthesis
Green Route for Lactic Acid Synthesis
Green Route for Maleic Anhydride
PROCESS INTENSIFICATION
The ultimate goal of PI is Guiding principles of PI
an ideal, intensified • Maximize the
processing system in effectiveness of
which intermolecular and
• Reactions proceed at a intramolecular events
maximum achievable • Give each molecule the
efficiency same processing
• All molecules undergo experience
the same processing • Optimize the driving
history forces and/or
• Hydrodynamic, heat- resistances at every
and mass-transfer scale and maximize the
limitations are specific surface areas
removed to which these forces
• Synergies resulting or resistances apply
from interrelations • Maximize the
between various synergistic effects of
operations and steps partial processes
are fully utilized
Avoid randomness in
chemical equipment
and replace it with
structure.
Transfer energy from the
source to the recipient in
the optimal way, including
the best form of energy
and energy transfer
mechanism.
Achieve synergy
by combining one
or more functions
(e.g., heat transfer
and mixing) in a
single device or
process step.
Manipulate time by
• Introducing an
controlled unsteady
state in a steady
state process to
attain operating
conditions that
improve process
performance
• Change process
duration
dramatically by
changing process
conditions
CYCLIC DISTILLATION
SEPARATION PROCESS INTENSIFICATION
DIVIDING WALL COLUMN
REACTIVE DIVIDING WALL COLUMN
HIGEE DISTILLATION – ROTATING ZIGZAG BED
SUMMARY OF SEPARATION PI TECHNOLOGIES
PROCESS INTENSIFICATION
GUIDING PRINCIPLES OF PI
–– Maximize the effectiveness of intramolecular and
intermolecular events (example: dynamically changing
conditions to attain kinetic regimes with higher conversion
and selectivity).
–– Provide all molecules the same process experience
(example: plug flow reaction with uniform, gradient-less
heating).
–– Optimize driving forces at all scales and maximize the
specific surface areas to which they apply (example:
increase transfer surface area through microchannel
designs).
–– Maximize synergistic effects from partial processes
(example: multifunctional reactors).
EQUIPMENT FOR PI – MICROFLUIDIC TECHNOLOGY
EQUIPMENT FOR PI – STATIC MIXERS
EQUIPMENT FOR PI – INTENSIFIED SEPARATION PROCESSES
MEMBRANE SEPARATIONS & HYBRID SEPARATIONS
CENTROFUGAL FIELD FOR PI
The essence of HiGee technology is replacing the gravitational field by a high
centrifugal field achieved by rotating a specially shaped rigid bed, typically a disk
with an eye in the center. The higher mass-transfer coefficients and higher flooding
limits allow the use of high surface-area packing. In this way, the momentum, heat
and mass transfer can be tremendously intensified.
HiGee distillation uses the rotating packed bed (RPB) concept in a high-gravity field
(100–1000 g) technology – claiming HETP values as low as 1–2 cm, about 3–6 times
higher throughput and an equipment volume reduction of 2–3 orders of magnitude
lower compared with that of conventional packed columns
