OPTIMIZATION OF CATALYTIC REFORMERS

 Introduction

 Types of Process Variables

 Effect of Operating Conditions

 Reformer Optimization

 Case Studies
 INTRODUCTION

 Catalyst Reformer is used to produce high-octane gasoline and aromatics

from naphtha.

 It is a major refinery unit

1. worldwide capacity 8.7 MBBLD (1990) is close to that of FCC
2. Reformate contributes upto 30% in the gasoline pool and is the most
important octane boosting stream.
3. Major source of BTX (32% of world’s benezene)

 Designing/Revamping/Operating this unit in optimum manners can have a

significant impact on refinery margin

 Catalytic reformers are designed to operate under flexible operating conditions

subject to various constraints.
 Optimization of operating conditions can boost the unit’s economy
significantly (upto ~110%)
 TYPES OF PROCESS VARIABLES

 What to optimize? (output variables)

1. Daily/Annual operating profit

2. Yield/Production Rate of
a) Reformate
b) BTX (Benzene, Toluene & Xylenes) in reformate
c) H2

3. Reformate quality
a) RON0/MON0 (unleaded research/motor octane no.)
b) RVP (Reid vapor pressure)
c) Benzene/Aromatic content

4. Residual cycle length or catalyst activity

 TYPES OF PROCESS VARIABLES

 What can be manipulated? (input variables)

1. Feed rate
3. Reactor inlet temperatures
4. Reactor / Separator pressure
5. H2/HC (hydrogen-to-hydrocarbon) ratio or recycle rate
6. Amount of cracked naphtha (that can be mixed with virgin naphtha)
7. Cl2/H2O (chlorine/moisture) dosing rate

 Hardware / Equipment constraints.

1. Reactor configuration - SR/CYCLIC/CCR (semi-regenerative / cyclic /
continuous catalyst circulation)
2. Catalyst type, loading and distribution
3. No. of reactors, feed/effluent heat exchanger type or area
4. Maximum RGC (recycle gas compressor) power
5. Maximum CHE/IHE (charge/inter heater) duties
 TYPES OF PROCESS VARIABLES

 Inputs constraints.
1. Feed rate
2. Recycle rate (or, H2/HC ratio)
3. Separator/Reactor pressure
4. Reactor inlet temperatures

 Outputs constraints.
1. Minimum RON0
2. Minimum cycle length

 Causes of process upsets or change in operating conditions.

1. Change in naphtha quality
a) IBP & FBP, or hydrocarbon compositions ( e.g., N+2A)
2. Change in operating objectives
 TYPES OF PROCESS VARIABLES
Daily Operating Margin (Rs/day) = (product –feed) value – operating cost
amount
Product value = (hydrogen + fuel gas + LPG) value quality
+ (benzene-toluene-xylene / reformate value) specification

Operating cost = (compressors’ power + charge and inter heater duty) cost
+ cycle length penalty

Octane No. (RON0 / MON0) -

Resistance to knocking (rumbling sound of uncontrolled ignition) that reduces
fuel efficiency.

RON0 is measured as percent of i-octane in n-heptane that has same knocking as

the unleaded fuel under standard experimental conditions.

MON0 is same as RON0 but measured under higher compression ratio.

 TYPES OF PROCESS VARIABLES
eformate Quality Specifications

ON0 – Current gasoline RON0 specification is 87-91.

It will be raised to 91-95 beyond 2005.
Since reformate has highest RON0 in gasoline pool, its RON0 should be much
higher than specified.

VP – Vapor pressure measured under standard condition.

Specification for gasoline is 35-100 Kpa.
Reformate RVP should be lower than this to allow blending of lighter
streams (e.g., light naphtha) into the gasoline pool.

enzene – Carcinogenic and toxic.

ontent Gasoline specification of 3-5 lv% (1-2 beyond 2005).

romatic – Toxic and produces smog.

ontent Gasoline specification 40-45 lv% (<35 beyond 2005).
 TYPES OF PROCESS VARIABLES
Feedstock quality

1. N+2A (naphthenic plus twice aromatics LV%) measured via PONA analysis.

2. Feed Composition measured in terms of carbon no. (e.g., C6, C7, C8, C9+) for
each major groups of hydrocarbons (e.g., paraffin, naphthene and aromatic)
via Gas Chromatograph (GC) or ASTM/TBP curve.

3. IBP / FBP (initial / final boiling point).

4. Mixing with cracked naphtha from FCC / Coker units.

5. presence of catalyst poisons.

 Empirical charts are often used to determine the necessary operating conditions.

 Model based simulation and optimization can provide the best answer.
 TYPES OF PROCESS VARIABLES

Feedstock quality (Empirical Charts)

95

N+2A = 80
C5+ Reformate Yield (vol.% )

90

85
N+2A = 60

80

N+2A = 40
75

70
90 91 92 93 94 95 96 97 98 99 100
RON0
 EFFECT OF OPERATING CONDITIONS
Reforming – 1. Naphthene dehydrogenation: NH  A + nH2
Reactions 2. Isomerization: n-P  i-P, NP-CH3  NH
3. Hydrocracking: P7  P4 + P3, P7  P6 + CH4
4. Dehydrocyclization: P  A + nH2
(P = Paraffin, NP = Cyclopentanes, NH = Cyclohexanes, A = Aromatic)

Reaction Relative Rate Heat of Reaction,

of Reaction cal/mole
Naphthene 100+ > 50000
Dehydrogenation
Isomerization 12 -1000 to –4000

Hydrocracking 4 -12000 to –15000

Dehydrocyclization 1 49000 to 64000

 EFFECT OF FEED RATE

 For a particular feed, product yields and qualities depend on the ratio of feed
rate to catalyst loading.

 LHSV is the volumetric ratio of feed rate (at 60oF & 1 atm) to catalyst
loading.
- Not a true residence time.
- Varies between 1-2 hr.-1

 WHSV is the mass ratio of feed rate to catalyst loading.

 Lower LHSV/WHSV
 Greater severity
 Greater reaction conversions including hydrocracking of paraffins and
coking (and vice versa).
 EFFECT OF FEED RATE

98
o
WAIT = 518 C
R ON0

94

90

-1

RON0 = 95
-5
WAIT (oC)

o
Base WAIT = 512 C
-9

-13

-17
20 18 16 14 12 10
-1
LHSV (hr. ) * 10
 EFFECT OF REACTOR TEMPERATURE
Reaction temperature must be kept high enough (> 460oC, normally 480oC) to
allow high equilibrium conversion of naphthenes and paraffins to aromatics, the
reactions being highly endothermic in nature .
 Differential (gradually increasing) catalyst loading and inter-heaters.

However, reaction temperature must not be too high (< 525 oC, normally 510oC) so
that elevated kinetic rates of hydrocracking and coke formation sharply reduces the
reformate yield and catalyst activity.

Fine control of reactors’ inlet temperature profile is essential to compensate for

changes in feedstock quality and catalyst activity.

WAIT, WABT = Average inlet and bed temperature respectively, averaged w.r.t.
reactor-wise catalyst distribution.

Higher WAIT/WABT  Greater severity

 Greater reaction conversions including hydrocracking of paraffins and coking
(and vice versa).
EFFECT OF REACTOR TEMPERATURE

100

95
RON0

90

85
485 490 495 500 505 510 515 520
o
WAIT ( C)
 EFFECT OF SEVERITY
Effects of Change in Reactor Severity (LHSV or WAIT)

RON0 C5+ Yield

93 85
99 78
RON0 H2, SCFB
92 630
100 790
RON0 Reformate RVP, psi
92 3.4
100 4.2
RON0 Reformate Benzene, LV%
92 2.1
100 2.8
RON0 Relative Cycle Length (21.4 atm)
90 1.0
100 0.2
 EFFECT OF REACTOR PRESSURE
Lowering of pressure increases equilibrium conversions in dehydrogenation and
dehydrocyclization reactions that involves a net increase in total moles .

Lowering of pressure also reduces H2 partial pressure and this in turn decreases the
hydrocracking of paraffins.

Lowering of pressure, however, increases coking (i.e., catalyst deactivation).

The reported reactor pressures (e.g., 15-22 & 4-7 atm for SR & CCR respectively)
are average values taking into account the pressure drops (e.g., 0.14-0.27 or 0.34-0.68
atm for each of the radial or axial reactors with fresh catalyst).

Lower reactor pressure  Greater RON0  Greater C5+ yield

 Greater H2 production
 Lower benzene conc.
 Lower RVP
 Greater coking (decreasing catalyst activity)
(and vice versa).
 EFFECT OF REACTOR PRESSURE

90

88

86
7.8 atm
C5+ Yield

84

82
14.6 atm
80

78 21.4 atm

76
90 92 94 96 98 100 102
RON0
 EFFECT OF REACTOR PRESSURE

Effects of Change in Reactor Pressure

Pressure, atm H2 Production, SCFB

4.4 1700
14.8 900
21.4 750
Pressure, atm Reformate Benzene conc., LV%
4.4 0.4
21.4 1.2
Pressure, atm Reformate RVP, atm
4.4 2.3
21.4 3.8
Pressure, atm Relative cycle length (RON0 = 90)
11.2 0.4
21.4 1.0
 EFFECT OF H2/HC RATIO

 Defined as moles of H2 in recycle to the total HC (hydrocarbon) moles in reactor

charge (excludes ~20% HC in recycle), normal ranges being 2 to 5.

 Lower H2/HC
 Lower recycle rate
 Lower energy cost
 Favors dehydrogenation reactions
 Increases Coking (decreasing catalyst activity)

(and vice versa).

 REFORMER OPTIMIZATION

Disturbances Changes

Feedstock’s Quality Operating Objective

Input / Output Hardware

Reformer
Constraints Limits

Best Operating Conditions ?

 REFORMER OPTIMIZATION
Why We Want to Optimize Reformer Operation?
Finding an operating point that will more closely meet the objective of
reformer operation than the current operating point.

Objectives of Reformer Optimization

 Maximizing the daily operating margin out of reformer unit.

 Coping with fluctuating demands of products, like, BTX and gasoline.

 Meeting stringent product quality specifications like RON0, benzene/aromatic

content and RVP of reformate.

 Minimize catalyst deactivation and hence increase the cycle length.

 Any combination of above objectives.

 REFORMER OPTIMIZATION
Issues in Reformer Optimization

 Profit may be defined in terms of multiple output variables (e.g., throughputs,

product qualities).

 There are multiple input variable, each of which influences all the output variables
although not to the same extent.

 There are hardware/equipment bounds, physical limits of input variables,

tolerable range of output variables.

Constrained, Multi-Variable & Nonlinear Optimization

 REFORMER OPTIMIZATION
Frequency Typical Benefits
Each 8-24 hr.

}
Off-Line Optimization (major changes and
disturbances)
10% more
Each 8-12 hr.
On-Line Optimization
(major changes and
disturbances)

Advanced Process Controllers $0.6-1.0 / m3

Each 1-5 min.
(Production Maximization, Octane Control,
(larger disturbances)
H2/HC Control, etc.)

PID Type Controllers ____

Each 1-20 sec.
(Feed Flow Control, Fuel Gas Flow Control,
(random disturbances)
Recycle Gas Pressure/Flow Control, etc.)
 REFORMER OPTIMIZATION
Reformer Plant Data Filtering
I/O Data

Data Reconciliation

Parameters Off-Line / On-Line

Model Updating
Optimizer

Constraints
Outputs
Inputs & Inputs &
Parameters Parameters
Process Model / Constraints
 REFORMER OPTIMIZATION
Data Filtering
Use Data when it appears that the process has reached a steady state
 Standard deviations of feed and product flowrates should be below a limit.

Eliminate outliers in all data

 Data values to be restricted within the maximum expected standard deviation.

Average out all data over a fixed period (usually, 2 hr.)

 Eliminate small random fluctuations in the data.

Examine the crucial data like recycle gas compositions, feed and reformate
compositions based on their expected ranges
 Amount of components in the recycle gas should fall exponentially with
increase in carbon number.
 Benzene / Toluene yields are normally more than higher aromatics.
 Component wise yield values should be within their expected range.
 REFORMER OPTIMIZATION
Data Reconciliation
 Eliminate data with gross error (instrument biases and process faults) using a
rigorous statistical methods like GLR (Generalized Likelihood Ratio) method.
g ( X , Z )  0; X  Measured & Z  Unmeasured
 
Model Linearization  AX  0  A Xˆ  e  0  AXˆ  Ae  r
E  (r )  bf & Cov (r )  ACov (e) AT  AQAT  V

 T
T  fi V r   fiTV 1 fi   
1 2

 Reconcile or adjust data to satisfy material balances (like, total and

carbon / hydrogen balances).
Min
( Xˆ  X )T Q 1 ( Xˆ  X )
X,Z
s.t.
g(X , Z )  0
X L  X  X U & Z L  Z  ZU
 REFORMER OPTIMIZATION

Data-Driven vs. Fundamental Models

 Data-driven model:
 Pre-defined model structure
 Can be fitted very quickly, provided necessary data are available
 Require huge amount of data, including feed/product component distributions
(i.e., not just on-line sensor data) collected at various times
 Existing plant data base in refineries may cover very narrow operating range
 Collecting more useful data by plant perturbations may not be allowed
 Collecting more useful data through pilot plant is costly
 Need to be updated continuously.

 Fundamental model:
 Can be fitted very quickly with just 2/3 data sets collected at various times
 Need update, but less frequently
 Arriving at the proper model structure is difficult.
 REFORMER OPTIMIZATION
Fundamental Models
 Rigorous dynamic model is difficult to solve, steady state model is normally used.

 Major reforming reactions are Naphthene Dehydrogenation, Isomerization,

Hydrocracking, Dehydrocyclization (details were shown in a previous slide)

 Apart from the usual frequency factor and activation energy, kinetic rate
expression may also include:
- Equilibrium constant to express reversibility of reactions
- Acid/Metal adsorption terms
- Catalyst activity rigorously calculated via a deactivation model

 Model equations include mass and energy balances for reactor, F/E exchanger and
product separation system.

 Calculation of recycle gas KW, reformate qualities, residual cycle length, daily
operating profit, etc.
 REFORMER OPTIMIZATION

I/O Data and Process Constraints

 Types of input / output data, hardware bounds, input limits and output constraints
were already discussed in a previous slide.

Model Update
 Needed if model predictions differ from plant data.

 Fundamental model parameters remain same as originally fitted.

 Only a few lumped parameters are tuned to primarily match:

 Reactor-wise dehydrogenation and cracking rates
 Equilibrium constants used in VLE calculations.
 REFORMER OPTIMIZATION
Optimizer
 SLP (successive linear programming) and SQP (successive quadratic
programming) are normally used.

 SQP is more efficient and faster in locating the optima anywhere in the feasible
region.

 In SQP, coefficients of a QP objective is recalculated at each new iteration.

Min  F ( z ) h( z )  0; g ( z )  0 


1
  
Min G   z F T z  zT  zz F  T h   T g z h   z hT z  0; g   z g T z  0
2 
Optimality Condition :
 z F   z h   z g  0; h( z )  0; g ( z )  0

 zz F  T h   T g  0
 REFORMER OPTIMIZATION CASE STUDIES
Optimization of a Commercial SR using CRESOP
(a software licensed by EIL & IIP)
Base Case Simulation
Feed Flow = 900 MT/day
Recycle Gas flow = 436.4 MT/day
No. of Reactors = 3
Catalyst Type = Bimetallic
Inlet Temperature of Successive Reactors = 498, 498, 498 oC
Pressure of Separator Drum = 17 bar

RGP HP = 2119.4 KW
CHT duty = 6.4 MMKcal/hr
1st IHT duty = 4.4 MMKcal/hr
2nd IHT duty = 2.0 MMKcal/hr
RON0 = 83.6
Cycle length = 8262.2 hr
Operating Margin = 2.50755425 x 106 Rs/day
 REFORMER OPTIMIZATION CASE STUDIES
Opr. Margin BTX Tonnage Maximization (X=920)
Maxm. Minm. Maximization Case A Case B (Y=3000)
Feed (MT/day) 900 (X) 850 900 904.7 (+4.7) 900
Recycle ( ” ) 440 400 440 (+3.6) 440 (+3.6) 440 (+3.6)
Sep. Press. (bar) 17 16 17 17 16.0 (-1.0)
1st Reac. in. oC 505 495 495 (-3) 495 (-3) 496.4 (-1.6)
2nd Reac. in. oC 505 495 495 (-3) 495 (-3) 495.8 (-2.2)
3rd Reac. in. oC 510 495 505 (+7) 504.4 (+6.4) 510 (+12)

RGP HP (KW) 2500 - 2105 (-94.4) 2122.3 (-77.1) 2146.7 (-52.7)

CHT MMKcal/hr 7 - 6.3 (-0.1) 6.3 (-0.1) 5.9 (-0.5)
1st IHT ” 5 - 4.3 (-0.1) 4.3 (-0.1) 4.3 (-0.1)
2nd IHT ” 3 - 2.7 (+0.7) 2.7 (+0.7) 3.0 (+1.0)
RON0 - 82 85.2 (+1.6) 85.2 (+1.6) 86.9 (+3.3)
Run Length (hr) 12000 8000 (Y) 8000 (-262.2) 8000 (-262.2) 6607.8 (-1654.4)

Margin (Rs/day) ___ ___ +3.32% +3.5% +4.7%

BTX (MT/day) ___ ___ ___ +3.1% +5.4%
 REFORMER OPTIMIZATION CASE STUDIES
Operating Margin Maximization:
Minm. Run length is the most important active constraint resulting in:
 highest separator pressure (to reduce catalyst deactivation)
 lowest inlet temperatures for the 1st two reactors (to reduce catalyst deactivation).

BTX Tonnage Maximization (Case A):

Minm. Run length is again the most important active constraint resulting in:
 highest separator pressure (to reduce catalyst deactivation)
 lowest inlet temperatures in the 1st two reactors (to reduce catalyst deactivation).

BTX Tonnage Maximization (Case B):

owering minm. run length has satisfied the following thermodynamic requirements:
lowest separator pressure (to increase BTX formation)
highest inlet temperatures in the 3rd reactor (to increase endothermic BTX
formation).
 REFORMER OPTIMIZATION CASE STUDIES
Optimization of a CCR
Base Case Simulation
Feed Flow = 1411 MT/day
Recycle Gas flow = 186 MT/day
Catalyst Flow = 0 Kg/hr
Inlet Temperature of Successive Reactors = 507, 507, 507 oC
Temperature & Pressure of Separator Drum = 37 oC & 3.3 Kg/Cm2
Temperature & Pressure of Recontacting Drum = 27 oC & 6.1 Kg/Cm2
Temperature & Pressure of LPG Absorber Drum = 26 oC & 13.3 Kg/Cm2

RGP HP = 2057 KW
CHT duty = 6.7 MMKcal/hr
1st IHT duty = 6.5 MMKcal/hr
2nd IHT duty = 3.6 MMKcal/hr
RON0 = 98.6
SR Cycle length = 58 hr
Operating Margin = 4.41856 x 106 Rs/day
 REFORMER OPTIMIZATION CASE STUDIES
Opr. Margin Maximization
Maxm. Minm. Case A Case B (X=1450)
Feed (MT/day) 1500(X) 1300 1500 (+89) 1450 (+39)
Recycle ( ” ) 220 150 205 (+19) 194 (+8)
Sep. Press. (bar) 5 3 3.3 (0) 3.7 (+0.4)
1st Reac. in. oC 510 495 498 (-9) 495 (-12)
2nd Reac. in. oC 510 495 505 (-2) 508 (+1)
3rd Reac. in. oC 510 495 510 (+3) 510 (+3)

RGP HP (KW) 3000 - 2245 (+188) 1980 (-77)

CHT MMKcal/hr 8 - 8.0 (+1.3) 7.0 (+0.3)
1st IHT ” 7 - 7.0 (+0.5) 7.0 (+0.5)
2nd IHT ” 5 - 4.1 (+0.5) 4.0 (+0.4)
RON0 - 98.5 98.5 (-0.1) 98.5 (-0.1)
Run Length (hr) - 24 60 (+2) 67 (+9)

Margin (Rs/day) ___ ___ +6.7% +3.7%

 REFORMER OPTIMIZATION CASE STUDIES
Operating Margin Maximization (Case A):
Maxm. feed rate, maxm. charge-heater duty, maxm. 1st inter-heater duty and minm.
octane no. are the most important active constraints resulting in:
 highest possible reformate production
 lower inlet temperatures in the 1st two reactors and highest inlet temperature in
the last reactor
 minimizing hydrocracking in the first two reactors (reformate is much more
valuable than light gases)
 completing conversion of naphthene to aromatics in the last reactor (minm.
octane no. must be achieved).

Operating Margin Maximization (Case B):

Lowering maxm. feed rate has the following effects:

 highest possible reformate production (lower than Case A)
 Better profile of reactor inlet temperatures is achieved (profit margin increases by
0.095% as compared to only 0.075% in Case A, for each MT increase in feed rate).
 REFERENCES
G. J. Antos, A. M. Aitani and J. M. Parera, "Catalytic Naphtha Reforming - Science &
Technology", Mercel Dekker, New York, 1995.
A. K. Datta, H. Singh, P. K. Sen, A. K. Saxena, G. Das, V. K. Kapoor, M. O. Garg, "Benzene
Management in Gasoline Using CRESOP", 11th Refinery Tech. Meeting, Hyderabad (India), 2000.
L. T. Biegler and J. E. Cuthrell, "Improved Infeasible Path Optimization for Sequential Modular
Simulators - II: The Optimization Algorithm", Comp. Chem. Engg., vol. 9, p.257, 1985.
N. L. Gilsdorf and R. H. Rachford, "Platforming in the Reformulated Gasoline Era", NPRA
annual meeting, Lousiana (USA), 1992.
M. J. Liebman, T. F. Edgar and L. S. Lasdon, “Efficient Data Reconciliation and Estimation for
Dynamic Process using NLP Techniques”, Comp. Chem. Engg., vol. 16, no. 10/11, p.963, 1992.
D. M. Little, “Catalytic Reforming”, PennWell, Tulsa (USA), 1985.
D. R. Mudt, T. W. Hoffman and S. R. Hendon, "The Closed-Loop Optimization of a
Semi-Regenerative Catalytic Reforming Process”, AIChE Meeting, March, Houston, 1995.
S. Narashimhan and R. S. H. Mah, "Generalized Likelihood Ratio Method for Gross Error
Detection", AIChE J., vol. 33, no. 9, p. 1514, 1987.
A. K. Saxena, G. Das and Harendra Singh, "Optimization of Semi-Regenerative Reformer - A
Case Study", Eighth Refinery Tech. Meeting, Chennai (India), 1995.
U. Taskar and J. B. Riggs, "Modeling and Optimization of a Semi-Regenerative Catalytic
Reformer", AIChE J., vol. 43, no. 3, p. 740, 1997.