Parameter estimation and

model discrimination of batch

solid-liquid reactors

Yajun Wang, Lorenz T. Biegler

Carnegie Mellon University

Mukund Patel, John Wassick

The Dow Chemical Company

Enterprise-wide Optimization Meeting

March 2017
 Problem Statement & Motivation
Agitator
• Batch reactor Solvent and reactant
materials
Vent
Solvent

Solid W
Preparation Cooling water Reactor
inlet jacket

Liquid X Solid-liquid Reaction

Cooling water
W(s) + X(l)  Y(s/l) + Z(s) outlet
Reactor discharge
• Unknown reaction mechanism – Surface reaction, dissolution, diffusion
Different particle shapes and sizes
Product effects
• Limited information – Lack of concentration measurements

An over-parameterized model without enough data

Problem Statement & Reactor Parameter Industrial Significance & 2
Motivation Modeling Estimation Case Study Potential Impact
 Reaction Mechanisms
Shrinking particle model (SPM) Dissolution model (DM)
cls b Assume dissolution is the rate limiting step.
c l

Reactant Reactant
Fluid reactant reactant

film

Liquid reactant diffuses Solid-liquid Solid particles Liquid–liquid

onto the particle surface reaction dissolve into solvent reaction

Solid product breaks off from reaction surface. Products precipitate into solid phase.
Reaction rate of SPM depends on liquid reactant concentration while DM doesn’t.
Problem Statement & Reactor Parameter Industrial Significance & 3
Motivation Modeling Estimation Case Study Potential Impact
 Batch Reactor Model
1/ a 11/ a aM
Total surface area is related to total amount and the shape of particles[1]. S   R N s 0 N s
s

s 0
Ea
dN s aM s 1/ as 11/ as  RT
SPM   s SR   s N s 0 N s k0e (cls )
dt  s R0
dN s aM s 1/ as 11/ as  RTEa • Parameters
DM  kS   s N N k0 e
dt  s R0 s 0 s

• Model indicator
F=0  DM
F>0  SPM

[1] Salmi, Tapio, et al. "New modelling approach to liquid–solid reaction kinetics: From ideal particles to real particles." Chemical
Engineering Research and Design 91.10 (2013): 1876-1889.
Problem Statement & Reactor Parameter Industrial Significance & 4
Motivation Modeling Estimation Case Study Potential Impact
 Parameter Estimation
Sensitivity coefficient matrix
Estimability evaluation
QR transformation with column permutation
Rank parameters by their individual variance contribution
Estimable?
NO
YES EVM formulation > WLS formulation
Simultaneous estimation Reduce • Data reconciliation
parameter set/
Simplify model • Parameter estimation

Estimation quality analysis Estimation covariance matrix

Reduced Hessian – confidence region
Small
Confidence NO Posterior probability share
interval? Bayes’ theorem
YES • Fitting
Posterior probability share • Number of parameters

Validation by unseen batch data

Model Validation Cross validation
Problem Statement & Reactor Parameter Industrial Significance & 5
Motivation Modeling Estimation Case Study Potential Impact
 Industrial Case Study
Solid-liquid batch reactor
• Batch k k = 1 … NS • Jacket temperatures • Reactor temperatures
• Inlet flowrates • Concentrations
• Measured input ukj* • Reactor weights
• Measured output ηki*
• Normally distributed measurements

 Estimability evaluation
Rank parameters by QRcp of scaled sensitivity matrix

• Parameter rankings at different points are different

• All parameters are included in the estimation

Problem Statement & Reactor Parameter Industrial Significance & 6

Motivation Modeling Estimation Case Study Potential Impact
 Industrial Case Study
 Simultaneous estimation -- EVM
Measured output errors Reactor temperature
0.8
Predict
0.75 Data
0.7
Measured input errors

Scaled temperature
0.65

0.6

0.55

0.5

0.45

• Reactor temperatures 0.4

• End-point concentrations 0.35 WLS

0.3
• Jacket temperatures 0 0.2 0.4 0.6
Scaled time
0.8 1

• Weights and flowrates

Reactor temperature
0.8
Predict
0.75 Data

• EVM does parameter estimation and data reconciliation 0.7

Scaled temperature
0.65

simultaneously 0.6

0.55
• Better output data fitting Accumulated squared errors of EVM is 0.5

reduced by 44% compared with WLS 0.45

0.4

• Intensive computational load EVM has 15771 variables and 0.35 EVM
0.3
13830 equation constraints 0 0.2 0.4 0.6
Scaled time
0.8 1

Problem Statement & Reactor Parameter Industrial Significance & 7

Motivation Modeling Estimation Case Study Potential Impact
 Industrial Case Study
 Estimation quality analysis

• Set Cb,X = Cs,X

• Set F = 0  dissolution model

• Fix parameter UA
Linearly temperature-dependent U

 Posterior probability share

Problem Statement & Reactor Parameter Industrial Significance & 8

Motivation Modeling Estimation Case Study Potential Impact
 Industrial Case Study
 Estimation results

 Model Validations
New data 9-fold cross validation
0.12
Estimated value in each iteration
Average of 9 estimations
Estimated value by all data
0.115

3
Parameter A 0.11

0.105


0.1

0.095
Unseen data
0.09
1 2 3 4 5 6 7 8 9
Iteration

Problem Statement & Reactor Parameter Industrial Significance & 9

Motivation Modeling Estimation Case Study Potential Impact
 Conclusions & Significance
• Discussed two potential models for a solid-liquid reaction in a batch
reactor
• Built a uniform dynamic model with an indicating parameter to
discriminate two mechanisms
• Introduced a parameter estimation procedure
• Applied parameter estimation to the solid-liquid batch reactor model
• Conducted model validation to examine the model capability of
predicting system behaviors

 Optimal control will be conducted based on estimated model to

reduce the batch time

Problem Statement & Reactor Parameter Industrial Conclusions & 10

Motivation Modeling Estimation Case Study Significance