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University of Nottingham Butanol Project - Design Guide 1

The process produces butanol from propylene via hydroformylation to produce an aldehyde, followed by hydrogenation to produce butanol. Propylene is reacted with syngas over a rhodium catalyst in three reactors to over 99% conversion to an aldehyde. The aldehyde vapor is hydrogenated in a fixed bed reactor over 99% to butanol, which is separated and refined in two distillation columns. Design guidelines are provided for equipment such as reactors, heat exchangers, pumps, and safety systems.

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0% found this document useful (0 votes)
73 views6 pages

University of Nottingham Butanol Project - Design Guide 1

The process produces butanol from propylene via hydroformylation to produce an aldehyde, followed by hydrogenation to produce butanol. Propylene is reacted with syngas over a rhodium catalyst in three reactors to over 99% conversion to an aldehyde. The aldehyde vapor is hydrogenated in a fixed bed reactor over 99% to butanol, which is separated and refined in two distillation columns. Design guidelines are provided for equipment such as reactors, heat exchangers, pumps, and safety systems.

Uploaded by

Tom Hart
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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University of Nottingham Butanol Project - Design Guide

1. Overview
The production of butanol in this process starts with propylene as the feedstock. Propylene undergoes
hydroformylation (also known as the oxo process) to produce an aldehyde before being hydrogenated
(alcohol process) to produce butanol.

2. Process description

2.1. Introduction
The hydroformylation reaction was discovered by Dr Otto Roelen in 1938 [1]. His experiments
resulted in a mixture of products that all contained oxo groups (i.e. carbonyl groups). In the oxo
process an olefin is reacted with syngas to produce an aldehyde. The oxo process has since enjoyed
great interest as it provides an easy route to make aldehydes from olefins. The catalyst used is
commonly a homogeneous catalyst Cobalt or Rhodium, whereby most modern processes use liganded
Rhodium. The ligand coordinates to Rhodium, thereby allowing a single atom to remain in solution.
Many ligands have been developed, and the latest ligand developed in the labs of Nottingham
University is called ‘MINIL’. The MINIL ligand is, like most modern ligands, a tetrakis-phosphite
type ligand, and when used for propylene hydroformylation, has the exceptional quality to produce a
normal- to iso-butyraldehyde ratio of 1000 to 1.

2.2. Oxo area


Propylene and Syngas are introduced in Reactor 1. The heat of reaction is removed by pumping the
reactor liquid through an external cooler. The liquid of Reactor 1 flows to Reactor 2, and from there to
Reactor 3 after which the conversion of propylene is over 99.6 %. The vent from Reactor 3 is
condensed by the reactor vent condenser. The uncondensables are passed on to flare or Gas Fuel
header, while the condensed liquid is returned to Reactor 3. The liquid from Reactor 3 flows to the
vaporiser. The vaporiser is a heat exchanger with condensate on the shell side. The vapour exiting the
vaporiser passes onto the hydrogenation area. Non-volatile catalyst and heavies are recovered in the
vaporizer tails as liquid and recycled to Reactor 1.

2.3. Hydrogenation area


The vapour leaving the vaporiser is superheated and compressed before injected into the VPH cycle
gas. The cycle gas with aldehyde is then heated in the VPH Interchanger and fed to the VPH
Converter. The VPH Converter is an adiabatic fixed bed catalytic reactor, converting over 99% of all
aldehydes to butanol. The stream leaving the converter is first cooled in the VPH Interchanger and
secondly cooled by cooling water such that butanol condenses. In the VPH Knock-Out Drum the
cycle gas is separated from the crude liquid product. The vapour from the VPH Knock-Out Drum is
returned to the VPH Compressor and heated in the VPH Interchanger before returning to the VPH
converter. The crude liquid butanol from the VPH Knock-Out Drum is forwarded to refining.
Hydrogen is consumed in the VPH Converter and has to be replenished continuously.
2.4. Refining area
The refining area consists of a two distillation columns in series, where butanol is separated from
lights and heavies. Lights contain mainly unconverted aldehyde and water. Heavies contain mainly
aldol condensation products. To limit the temperature in the reboiler the heavies concentration in the
tails is limited to about 50w%. The lights and heavies from the refining column are sent to waste
liquid fuel.

3. Proposal design guide


The following sections contain design parameters and guidelines to be used when preparing the
proposal.

3.1. Oxo reactors


• Operating pressures: 19, 18, 17 bara for Oxo Reactors 1, 2, and 3 respectively
• Operating temperature: 95-100°C
• Conversion of propylene to aldehyde: 90 % in each reactor
• Conversion of propylene to propane: 0.5 % in each reactor
• Conversion of propylene to heavies (C12HxO3): 0.1 % in each reactor
• Ungassed liquid level: 80 %
• Ungassed Liquid Residence time: 30 mins each
• Liquid expansion on gassing: <25%
• L/D ratio: ~3 m/m
• Rhodium concentration: 50 ppmwt
• Ligand/Rhodium ratio: 3.0 mol/mol
• Partial pressure H2: 10 bar
• Partial pressure CO: 4 bar
• Agitator power: 1.5 kW/m3
• MINIL Molecular weight: 900 kg/kmol
• MINIL consumption: 0.04 kg/day/per m3 reactor volume
• MINIL price: 1000 $/kg

The external cooler for Oxo Reactor 1 uses cooling water and operates with LMTD = 15 °C. The
Reactor 3 vent should be less than 3% of the SynGas feed.

3.2. Vaporisation
• Vaporiser Feed to Tails ratio: 5 kg/kg
• Vaporiser exit temperature: 130°C
• Vaporiser operating pressure: 1.5 bara
• LMTD design: 20°C

3.3. Butanol conversion


• Superheater provides 20°C of superheat
• Converter conversion Bal to butanol: 99 % at start of life (SOL), 90 % at end of life (EOL)
• Converter conversion Bal to 2-ethyl-hexanol: 0.2 to 1.0 % (SOL to EOL)
• Converter maximum superficial velocity: 0.5 m/s
• Converter catalyst bed height: 6 m
• Converter maximum diameter: local regulations
• Converter catalyst size: 7 mm diameter spheres
• Converter bulk density: 1200 kg/m3
• Converter particle density: 2100 kg/m3
• Converter Inlet Pressure: 5.5 bara
• Converter pressure drop: 0.2 bar
• Converter exit temperature: <250°C
• Interchanger LMTD: 15°C
• Cooler exit temperature: 45°C
• VPH Knock-Out Drum vapour exit pressure: 4.5 bara
• VPH Knock-Out Drum hold up time: 10 min
• VPH Cycle Gas Compressor to overcome cycle gas pressure drop + 0.2 bar
• Cycle gas to Bal ratio: 15 mol/mol
• Cycle Gas Hydrogen molar fraction: > 60%

3.4. Refining
Design rules

spec unit Lights Column Heavies Column


Pressure in the top bara 1.5 1.3
Number of trays # Tbd Tbd
Feed tray # Tbd Tbd
Condenser Temp °C 10 °C below dewpoint 10 below dewpoint
Vent Condenser Temp °C 35 -
Reflux Ratio w fraction Tbd Tbd
Reboiler Duty kJ/kg feed 300 450
Heavies conc w% < 50 butanol

Generic Column Design rules

• Tray spacing: 350 - 600 mm


• Tray efficiency: ~80 %
• Maximum approach to flooding for valved trays: 80 %
• Tray type: valved or sieve
• Max tray open area: 12 %
• Column L/D: < 16 m/m
• Duty ratio Condenser/Vent Condenser ~ 10/1
• Generic Liquid levels guide (Column sump and Receiver)
o Level Alarm High High (trip) to flood: 2 minutes
o Level Alarm High to LAHH: 2 minutes
o Normal Liquid Level to LAH: 3 minutes
o NLL to LAL: 3 minutes
o Level Alarm Low to LALL: 2 minutes:
o Level Alarm Low Low (trip) to empty: 2 minutes
• Bottoms temperature: ~ 130-140°C

3.5. Heat exchangers


The type of heat exchanger will be selected by the student and the associated area requirement must
be determined.

Heat transfer coefficients:

• Reboilers: 1000 W/m2K


• Condensers: 400 W/m2K
• Vapour/vapour: 200 W/m2K
• Liquid/liquid: 800 W/m2K
• Vapour/liquid: 250 W/m2K.

Fouling factors:

• Steam side: 0.00009 m2K/W


• Cooling water: 0.000175 m2K/W
• Process side: 0.000344 m2K/W.

3.6. Pumps
All pumps are supplied in couples, i.e. 1 operating 1 installed standby. For pump calculations the
pressure drop, power requirement and motor requirement are to be determined. Assume a motor
efficiency of 80% where the absorbed power is below 5kW. Above assume a motor efficiency of
90%. Standard motor sizes are: 450, 425, 400, 375, 355, 315, 280, 250, 225, 200, 185, 160, 150, 132,
110, 90, 75, 55, 45, 37, 30, 22, 18.5, 15, 11, 7.5, 5.5, 4, 3, 2.2, 1.5, 1.1,(below 1.0 specify 1.0). Above
450kW are custom.

3.7. P&ID
The piping and instrumentation diagram must include the following:

• All process pipelines (major, minor, bypass etc.)


• Instruments (temperature/pressure indicator, flow meters, level controllers, etc.)
• Valves (isolation, emergency shutoff, pressure relief, bypass, non-return, anti-surge etc.)

3.8. HAZOP
A hazard and operability study should include:

• Identification of all hazards and problems that may affect operation such as
o Materials
o Operating conditions
o Fire/explosion
• The likelihood and consequences of a hazard’s occurrence
• Necessary measures and safeguards required to mitigate hazards
o Trip instruments and controls (high/low level/flow/temperature alarms etc.)
o Trip valves positioning and sizing (relief, non-return, anti-surge etc.)
o Maintenance procedures

3.9. Plot plan


The plot plan should include two drawings: an aerial layout of the plant and a side elevation drawing.
It should include all vessels, exchangers and pumps, using their calculated dimensions. The following
factors must be considered:

• Safety
• Process requirements
• Operational access (min. 1.2 m width for humans)
• Ease of construction
• Separation distances for safety (see industry standards such as NFPA 400). Typical
separation distances include
o Control room from process equipment: 15 m
o Flammable equipment from main plant road: 15 m
o Buildings from process equipment: 60 m
o Flare from process equipment: 60 m
• The positioning of a pipe rack to carry major lines
• Pumps should be located at grade (ground level) with a minimum suction distance, and
protected from freezing.
• Columns require road access for a crane and a laydown area
• Compressors should be housed, and be close to knockout drum
• The storage and spacing of tanks and catalysts. Tank spacing codes include NFPA 30 and
Institute of Petroleum code
• Bund walls are required for tanks that contain liquids at atmospheric conditions.

An example of a basic plot plan at grade level is provided for reference. Separation distances in this
example do not meet requirements. Plot plans for grade, any upper levels, and side elevations must be
provided.

3.10. Materials of construction


Dissolved Iron is a strong promotor for heavies formation from aldehydes. Therefor, all equipment in
the oxo area in contact with the process fluids are made of stainless steel, typically 304L grade or
better.

All equipment of the hydrogenation and refining areas are made of carbon steel. Removable internals
are Stainless steel.

Storage tanks for aldehyde are Stainless steel, others are carbon steel.
3.11. Storage
Storage tanks to be supplied for catalyst hold up and product shift storage.

• Catalyst Hold Tank, 1 tank, volume of one reactor liquid


• Butanol product, 2 tanks, 95% full at 8 hours of production.

Aldehyde tanks require Nitrogen blanket.

4. References
[1] VAN LEEUWEN, P.W.N.T.M, and C. CLAVER. 2002. Rhodium Catalyzed Hydroformylation.
London: Kluwer Academic

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