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(
HDPE
H C H
H C H
H C H
H C H
H C H
)n
LDPE
If there is no branching (left), it is linear high density polyethylene - HDPE Branching results in low-density polyethylene LDPE (right) The ratio of hydrogen and ethylene in the reactor feed is an important variable for controlling the density of the polymer
Value
Value
Use PMS Speed to Replace Multiple PGCs Use PMS Precision to Improve Control 1% improvement in yield of LLDPE worth $13K per day on a typical unit
Olefin furnace
Hydrocarbon feed pyrolized with steam at 750-900 C in tubular furnace Gas feed (ethane, propane)
C2H6 CH2=CH2 + H2 C3H8 CH3CH=CH2 + H2
To gas analyzer
Residence time 0.08-0.25 seconds, pressure 175-240 kPa Effluent product stream quenched by heat exchanger Various components (particularly ethylene) separated out by further processes Need to avoid undesired reactions
Dehydrogenation to acetylene, MAPD Condensation to cyclo-diolefins & aromatics Coking
These are used to control severity & selectivity so that most profitable gas composition is sent to the recovery section
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P = Kp
(yH2)(yC2H4)
P = hydrocarbon partial pressure Kp = equilibrium constant for ethane dehydrogenation reaction at coil outlet temperature (COT) y = mole fraction of constituent in coil effluent
(yC2H6)
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Open-loop
According to the Technip SPYRO Team GCs are too slow and unreliable For closed-loop control
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rC
AC2H4exp [-Ea,C2H4]
RT
rC
= CH2 CCH4
KiCi
i=1
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Real-Time Optimization (RTO) models change severity set-points after taking into account feedstock analysis, feedstock costs, market conditions (or down-stream requirements) and energy prices
* Stone & Webster technology naphtha feedstock
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MS mean 13.4136 0.0011 28.6200 0.3768 27.5646 4.7831 0.0188 0.2928 12.7321 0.3246 2.9312 3.5980 0.3046 0.9627 0.7922 0.5557 0.1951 0.8675 0.7501 0.2226 0.4439 0.2489
GC mean
12.9908 0.3879
MS analyzes 22 components in 30 seconds 3 minute sample interval 1 MS for 5 furnaces GC analyzes 5 components in 3-6 minutes 1 GC per furnace MS precision ~ 0.1% relative GC precision ~ 0.5% relative Additional extended analysis (slow) GCs needed to provide model input data
Primary control requirement is to optimize product slate and minimize coking due to excessive carbon radicals
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Although one MS can replace all 15 GCs, in practice a 2nd unit is typically provided for redundant operation
2.5 minute sample interval (99% of the time)
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GC
Online, near real-time analysis permits tight control of cracking severity in order to maximize the yield of target olefins Advanced control models developed using MS data more accurately predict coke deposition rates which minimizes energy consumption (steam and fuel gas) Tight severity control extends the operating hours of each furnace thereby increasing annual production of olefins High reliability and very low maintenance result in much lower total cost of ownership compared to multiple-GC alternative
MS
Ethylene mol%
On a typical ethylene unit (750 ktpa) 1% increase in ethylene yield worth $20k per day
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6 Furnaces chosen for the test: 3, 5, 6, 7,11 & 12 GC Cycle Time = 9 min MS Cycle Time = 3 min
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Membrane filter
Process line
Bypass exhaust
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24 hour cracking severity (propylene/ethylene) following simultaneous calibration of MS (brown) and GC (blue)
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This test established a 5-day calibration interval for the GC. 17 days is not nearly enough to assess the stability of the mass spectrometer.
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90 second measurement interval for extended analysis to include hydrogen and speciation to C6
All furnaces connected to all Mass Specs for 100% availability
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Opportunity Cost
Assumptions Olefins production 700,000 tonnes per year @ $1,000 pt $700M pa Each 1% improvement in yield = $7M pa The improvement in the yield of ethylene and other high-value hydrocarbons is expected to be at least 1% when MS monitoring replaces GC due to the extended analysis, superior precision, stability and availability If we add the 10-year opportunity cost to the TCO10 in the 9-furnace example we get the following cost comparison:
Summary
Tight control of cracking severity requires online furnace effluent analysis to maximize profit Furnace effluent analysis cycle time needs to be 3 minutes or less to track process kinetics Prima PRO provides Superior precision (x5) Extended analysis (speciation to C6) Higher availability (100% with redundant installation) More flexible configuration (configured with software rather than hardware) Prima PRO provides rapid ROI and low TCO10 due to 3-year maintenance interval and 3-4 hour PM All Prima PROs are shipped with performance guarantee and 3year parts & labour warranty with travel expenses also covered for the first 12 months, significantly reducing risk of switching to MS
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