Designing optimal mixtures using generalized disjunctive programming: Hull relaxations

A general modeling framework for mixture design problems, which integrates Generalized Disjunctive Programming (GDP) into the Computer-Aided Mixture/blend Design (CAMbD) framework, was recently proposed (S. Jonuzaj, P.T. Akula, P.-M. Kleniati, C.S. Adjiman, 2016. AIChE Journal 62, 1616–1633). In this paper we derive Hull Relaxations (HR) of GDP mixture design problems as an alternative to the big-M (BM) approach presented in this earlier work. We show that in restricted mixture design problems, where the number of components is fixed and their identities and compositions are optimized, BM and HR formulations are identical. For general mixture design problems, where the optimal number of mixture components is also determined, a generic approach is employed to enable the derivation and solution of the HR formulation for problems involving functions that are not defined at zero (e.g., logarithms). The design methodology is applied successfully to two solvent design case studies: the maximization of the solubility of a drug and the separation of acetic acid from water in a liquid-liquid extraction process. Promising solvent mixtures are identified in both case studies. The HR and BM approaches are found to be effective for the formulation and solution of mixture design problems, especially via the general design problem

Application of the SAFT-γ Mie group contribution equation of state to fluids of relevance to the oil and gas industry

Calculated data for all the figures presented in publication

Computer-aided design of optimal environmentally benign solvent-based adhesive products

The manufacture of improved adhesive products that meet specified target properties has attracted increasing interest over the last decades. In this work, a general systematic methodology for the design of optimal adhesive products with low environmental impact is presented. The proposed approach integrates computer-aided design tools and Generalised Disjunctive Programming (GDP), a logic-based framework, to formulate and solve the product design problem. Key design decisions in product design (i.e., how many components should be included in the final product, which active ingredients and solvent compounds should be used and in what proportions) are optimised simultaneously. This methodology is applied to the design of solvent-based acrylic adhesives, which are commonly used in construction. First, optimal product formulations are determined with the aim to minimize toxicity. This reveals that number of components in the product formulation does not correlate with performance and that high performance can be achieved by investigating different number of components as well as by optimising all ingredients simultaneously rather than sequentially. The relation between two competing objectives (product toxicity and concentration of the active ingredient) is then explored by obtaining a set of Pareto optimal solutions. This leads to significant trade-offs and large areas of discontinuity driven by discrete changes in the list of optimal ingredients in the product

On the optimal design of gas-expanded liquids based on process performance

AbstractGas-expanded liquids (GXLs) are mixed solvents composed of an organic solvent and a compressible gas, usually carbon dioxide (CO2) due to its environmental and economic advantages. The best choice of GXL, as defined by the specific organic solvent and the CO2 composition, depends strongly on the process in which the solvent is to be used. Given the large range of possible choices, there is a need to predict the impact of GXL design on process performance from economic and environmental perspectives. In this work, we present a design methodology in which limited experimental data are used to build a predictive model which allows a wider design space to be assessed. The proposed methodology for the integrated design of CO2-expanded solvent and process is applied to the Diels–Alder reaction of anthracene and 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD). Three organic co-solvents are studied: acetonitrile, methanol and acetone. Given that the process cost is sensitive to the operating pressure and reactor volume, a trade-off between reaction rate constant and solubility is required in order to design an optimal process from a cost perspective. From a total cost perspective and in terms of energy consumption, it is found that designs with small amounts of CO2 or, in the case of acetone, without any CO2, offer the best performance. However, CO2 use is found to lead to a significant reduction in organic solvent inventory, up to 70 % in some cases. In this work the importance of taking multiple performance criteria, including process metrics, into account when designing GXLs is demonstrated

A QM-CAMD approach to solvent design for optimal reaction rates

The choice of solvent in which to carry out liquid-phase organic reactions often has a large impact on reaction rates and selectivity and is thus a key decision in process design. A systematic methodology for solvent design that does not require any experimental data on the effect of solvents on reaction kinetics is presented. It combines quantum mechanical computations for the reaction rate constant in various solvents with a computer-aided molecular design (CAMD) formulation. A surrogate model is used to derive an integrated design formulation that combines kinetics and other considerations such as phase equilibria, as predicted by group contribution methods. The derivation of the mixed-integer nonlinear formulation is presented step-by-step. In the application of the methodology to a classic SN2 reaction, the Menschutkin reaction, the reaction rate is used as the key performance objective. The results highlight the tradeoffs between different chemical and physical properties such as reaction rate constant, solvent density and solid reactant solubility and lead to the identification of several promising solvents to enhance reaction performance

Advanced thermodynamic and processing modelling integration for amine scrubbing in post-combustion CO~2~ capture

The reduction in CO~2~ emissions from anthropogenic sources has become a topic of widespread interest over the past number of years. As the power generation sector is by far the largest stationary-point-source of CO~2~, being responsible for approximately 35% of total global CO~2~ emissions^1^ this question has special relevance for this industry. As the inclusion of carbon capture facilities incurs a significant energy penalty on the efficiency coal-fired power-stations, there is a strong requirement for the improvement of these systems in terms of the minimisation of operation and maintenance costs, capital costs and the maximisation of efficiency and flexibility. This last issue has relevance for start-up times and ramp-rates. Post-combustion capture methods based on the chemisorption of CO~2~ in aqueous amine solutions are among the most mature and accepted technologies for CO2 capture from power plants^2^. However, amines are complex, associating solvents requiring a sophisticated thermodynamic model, capable of modelling the hydrogen bonding interactions that occur in these systems. One such model is provided by the statistical associating fluid theory (SAFT^3^). This is a molecular approach, specifically suited to hydrogen-bonding, chain-like fluids. In this contribution we use the SAFT approach for potentials of variable range (SAFT-VR^4^) to model the thermodynamics and phase equilibria of a number of amines including ammonia and monoethanolamine. The molecules are modelled as homonuclear chains of tangentially bonded square-well segments of variable range, and a number of short-ranged off-centre attractive square-well sites are used to mediate the anisotropic effects due to association in the fluids. We also determine values of the binary parameters for mixtures and then use these parameters to predict the phase equilibria of amine+water, amine+carbon dioxide as well as water+carbon dioxide mixtures. We then consider the phase equilibria of the ternary mixtures of amine+water+carbon dioxide and finally that of quaternary mixtures of amine+water+carbon dioxide+nitrogen. A good quantitative understanding of the phase behaviour of these quaternary mixtures is essential for accurate modelling of absorption processes for carbon dioxide capture. 

1. Steeneveldt, R., Berger, B. & Torp, T.A., ChERD, 84(A9): 739-763, 2006
2. Rao, A.B.; Rubin, E.S., 2002. A Technical, Economic, and Environmental Assessment of Amine-Based CO2 Capture Technology for Power Plant Greenhouse Gas Control. Environ. Sci. Technol. 36, 4467-4475
3. Chapman, W.G., Gubbins, K.E., Jackson, G. & Radosz, M., Ind. Eng. Chem. Res., 1990. 29, 1709-1721
3. Gil-Villegas, A., Galindo, A., Whitehead, P. J., Mills, S. J. & Jackson, G., J. Chem. Phys. 106 (10), 8 March 199

Rationalising the difference in crystallisability of two sulflowers using efficient in silico methods

The molecular structures of the first and second generation sulflowers, sulflower and persulfurated coronene (PSC), are remarkably similar: carbon ring structures decorated with sulfur atoms, without any additional moiety