Statistical modelling of the amination reaction of cyclohexanol to produce cyclohexylamine over a commercial Ni-based catalyst

Abstract Multivariate linear regression (MLR) models between the operating conditions and the performance parameters for the amination reaction of cyclohexanol (CHOL) with NH3 as aminating agent and in the presence of H2, using a commercial Ni-based catalyst, were established. The regressors were chosen according to a stepwise variable selection approach that only significant and non-redundant input variables were selected. The obtained models (related to CHOL conversion and yields for the more relevant products) were statistically significant with good fittings. Moreover, the models also reveal to act as good predictors, by cross validation and external validation. Nevertheless, models fitted to cyclohexyldeneaniline (CHONE) formation still present opportunities for improvement, given their poorer prediction performance. Sensitivity analysis of the developed models confirm the tendencies observed by Exploratory Data Analysis (EDA) indicating that the established relationships are able to translate the experimental observations. Therefore, the models can be used for process optimization purposes and scale-up methodologies.

[1]  D. Hamby.  A review of techniques for parameter sensitivity analysis of environmental models , 1994, Environmental monitoring and assessment.

[2]  Nola D. Tracy,et al.  Multivariate Control Charts for Individual Observations , 1992 .

[3]  Jichun Wu,et al.  Identification of the dominant hydrological process and appropriate model structure of a karst catchment through stepwise simplification of a complex conceptual model , 2017 .

[4]  Tiago J. Rato,et al.  Multiresolution interval partial least squares: A framework for waveband selection and resolution optimization , 2019, Chemometrics and Intelligent Laboratory Systems.

[5]  R. Sundberg,et al.  Advanced Organic Chemistry. Part B: Reactions and Synthesis. Fourth Edition , 2001 .

[6]  Raymond H. Myers,et al.  Probability and Statistics for Engineers and Scientists. , 1973 .

[7]  Zhongheng Zhang,et al.  Variable selection with stepwise and best subset approaches. , 2016, Annals of translational medicine.

[8]  A. Baiker,et al.  Catalytic Synthesis of Higher Aliphatic Amines from the Corresponding Alcohols , 1985 .

[9]  N. Draper,et al.  Applied Regression Analysis. , 1967 .

[10]  Elizabeth A. Peck,et al.  Introduction to Linear Regression Analysis , 2001 .

[11]  D. Butler,et al.  Stepwise pH control to promote synergy of chemical and biological processes for augmenting short-chain fatty acid production from anaerobic sludge fermentation. , 2019, Water research.

[12]  H. Hamada,et al.  Vapor-Phase Amination of Cyclohexanol over Silica-Supported Platinum Group Metal Catalysts , 1987 .

[13]  R. Sundberg,et al.  Aromatic Substitution Reactions , 2007 .

[14]  M. Keller,et al.  Amination of cyclohexanone and cyclohexanol/cyclohexanone in the presence of ammonia and hydrogen using copper or a group VIII metal supported on a carrier as the catalyst , 2000 .

[15]  Marco S. Reis,et al.  Data-driven methods for batch data analysis - A critical overview and mapping on the complexity scale , 2019, Comput. Chem. Eng..

[16]  Jorge Otávio Trierweiler,et al.  Are complex black-box models for Permanent Downhole Gauge pressure estimation necessary? , 2019 .

[17]  J. Fox,et al.  Applied Regression Analysis and Generalized Linear Models , 2008 .

[18]  A. Khataee,et al.  Mechanical production and sonocatalytic application of Cu2S nanoparticles for degradation of isopropylxanthic acid: Kinetic modeling via white and black box methods , 2019, Journal of Molecular Liquids.

[19]  Rojali,et al.  Stepwise Optimization for Model of Integrated Batch Production and Maintenance Scheduling for Single Item Processed on Flow Shop with Two Machines in JIT Environment , 2017, ICCSCI.

[20]  Shuainan Liu,et al.  An Efficient Method for the Production of Cyclohexylamine from Cyclohexanone and Ammonia over Cu-Cr-La/γ-Al2O3 , 2015 .

[21]  M. Ribeiro,et al.  Amination Reaction of Cyclohexanol over a Commercial Ni-Based Catalyst, Part I: Influence of Operating Conditions , 2020 .

[22]  M. Ribeiro,et al.  Amination of Cyclohexanol over a Ni‐Based Catalyst – Part II: Catalyst Stability and Reaction Pathway , 2021 .

[23]  H. Neumann,et al.  The Catalytic Amination of Alcohols , 2011 .

[24]  H. Neumann,et al.  An efficient and general synthesis of primary amines by ruthenium-catalyzed amination of secondary alcohols with ammonia. , 2010, Angewandte Chemie.

[25]  M. T. Mastura,et al.  Material selection of natural fibre using a stepwise regression model with error analysis , 2019, Journal of Materials Research and Technology.

[26]  S. Chatterjee,et al.  Regression Analysis by Example , 1979 .

[27]  David A. Freedman,et al.  Statistical Models: Theory and Practice: References , 2005 .

[28]  Jeffrey S. Simonoff,et al.  Handbook of Regression Analysis , 2012 .

[29]  Akhil Garg,et al.  Stepwise approach for the evolution of generalized genetic programming model in prediction of surface finish of the turning process , 2014, Adv. Eng. Softw..

[30]  Arthur Jutan,et al.  Grey-box modelling and control of chemical processes , 2002 .

[31]  Ulf Leser,et al.  Predictive performance modeling for distributed batch processing using black box monitoring and machine learning , 2018, Inf. Syst..