The number of design and processing requirements in the chemical and biochemical industries are increasing to
adapt to rapidly changing markets and the global competition, as well as to shift toward more sustainable
production and to meet the need for new and innovative products. Hence, more efficient processes are needed.
This need led to the introduction of process intensification. Process intensification is a tool for the targeted
enhancement of involved phenomena at different scales to achieve a targeted benefit (Lutze et al., 2010b). The
four scales for these systems are the
Process/Plant level
The operation and equipment level
The phase and functional level, and
fundamental and molecular level (Lutze et al., 2010b; Freund and Sundmacher, 2008).
Especially for equilibrium reactions like esterification, ester hydrolysis and etherification, the combination of
reaction and separation within one zone of a reactive distillation column is a well-known alternative to
conventional processes with sequential reaction and separation steps (Hiwale et al., 2004; Kaibel et al., 2005).
Hybrid separations integrate two different unit operations that complement each other to solve a defined
separation task (Franke et al., 2008). This arrangement enables the use of each unit operation in the operating
window in which it outperforms all others.
The overall goal in the reaction step is to achieve the highest production efficiency and yield of the desired
product at the lowest possible cost during safe operation. High efficiency and selectivity may also simplify the
downstream separation steps. The overall goal of the separation steps is to maximize the purity and recovery of
the products at the lowest costs.
This paper aims to provide an overview of past and current research regarding reactive and membrane-assisted
distillation, including pervaporation and vapor permeation, to provide a personal opinion of future research
trends, needs and challenges for these technologies.
Identifying a common operating window between the reaction and separation that provides acceptable and controllable
reaction rates and appropriate volatilities to ensure high concentrations of reactants and low concentrations of products
in the reactive zone is difficult.
Multiple motivations underlie the application of this concept (Sundmacher and Kienle, 2003; Taylor and Krishna, 2000;
Gorak et al., 2007):
Improved Conversion.
Circumventing/Overcoming of azeotropes.
Reduced side-product formation.
Direct heat integration and avoidance of hot spots.
Capital savings.
Decreased catalyst amount.
Reactive distillation is used with reversible, liquid phase reactions. Suppose a reversible reaction
had the following chemical equation :
For many reversible reactions the equilibrium point lies far to the left and little product is
formed:
However, if one or more of the products are removed more of the product will be formed because
of Le Chatlier's Principle :
Removing one or more of the products is one of the principles behind reactive distillation.
Saturday, November 18,
CHEMICAL ENGINEERING DEPARTMENT, MNNIT 6
2017
MEMBRANE ASSISTED SEPARATION PROCESS
Membrane technologies have recently emerged as an additional category of separation processes to the well-
established mass transfer processes. Membrane separation technologies offer advantages over existing mass
transfer processes.
In membrane separations: (i) the two products are usually miscible, (ii) the separating agent is semipermeable
barrier, (iii) a sharp separation is often difficult to achieve.
In its simplest form, is an energy efficient combination of membrane permeation and evaporation.
It's considered an attractive alternative to other separation methods for a variety of processes.
For example, with the low temperatures and pressures involved in pervaporation, it often has cost and
performance advantages for the separation of constant-boiling azeotropes.
A concentrate and vapor pressure gradient is used to allow one component to preferentially permeate across the
membrane.
A vacuum applied to the permeate side is coupled with the immediate condensation of the permeated vapors.
Pervaporation is typically suited to separating a minor component of a liquid mixture, thus high selectivity
through the membrane is essential.
Pervaporation can used for breaking azeotropes, dehydration of solvents and other volatile organics,
organic/organic separations such as ethanol or methanol removal, and wastewater purification.
As consequence of the negative impacts that MTBE has on the environment, ETBE has become a popular alternative
oxygenate additive for gasoline. In addition, it has higher heating value and lower oxygen content, lower water
solubility and faster degradation in soils (Bardin et. al., 2014).
ETBE is produced on industrial-scale by a reversible reaction of isobutene (IB) and ethanol (EtOH) with a strong
acidic macroporous ion exchange resign in liquid phase at 10 bar.
A drawback in the conventional ETBE manufacture is the energy intensive product recovery process, making ETBE
expensive. The purification process of ETBE involves the separation of ETBE, mixed C4 hydrocarbons and unreacted
ethanol. Unfortunately, the unreacted ethanol forms azeotropic mixtures with ETBE that are difficult to separate by
distillation.
While distillation provides large capacities and simple operation, membranes potentially offer a high selectivity and
low energy consumption, as well as a compact and modular design (Sirkar, et. al., 2015).
4 8 + 2 6 6 14 ------------------------------------------- (1)
4 8 + 2 4 10 ---------------------------------------------- (2)
24 8 8 16 -------------------------------------------------------- (3)
Eq. 1 represents the etherification reaction, Eq. (2) represents the hydration of isobutene to form tert-butyl alcohol, and
Eq. (3) represents the dimerization reaction of isobutene to form di-isobutene.
The etherification reaction is limited by the thermodynamic equilibrium in the range of temperatures typically used in
the industrial field. Thus, the equilibrium conversion at 343 K for a stoichiometric mixture of reactants is only 84.7%
(Jensen, et. al., 1995; Sneesby, et. al., 1997).
The secondary reaction of isobutene dimerization (Eq. (3)) is favored at low concentration of ethanol and at high
temperature and is also equilibrium limited (Rehfinger et. al., 1990).
In the case of ethanol/ETBE mixtures, these compounds form an azeotropic mixture containing 20.4 wt% ethanol at
94.7 kPa and 65 C (Rarey, et. al., 1999).
Fig. The conventional process for the production of ETBE with pressure swing distillation for product purification.
Fig. Schematic diagram of the reactive distillation process for ETBE production
The complexity of this process is due to the occurrence of two azeotropes, one between methanol and methyl acetate
(at 66.7 mol% methyl acetate) and one between n-butyl acetate and butanol (at 78.01 mol% butanol).
A single reactive distillation column can replace conventional multi-unit processes that require five times more energy
and capital investment (Taylor and Krishna, 2000).
The thermally coupled distillation (TCD) technique has proven to bean attractive method for reducing both the energy
and capital costs of distillation processes. TCD sequences are obtained through the implementation of interconnecting
streams (one in the liquid phase and the other in the vapor phase) between two columns.
Each interconnection replaces one condenser or one reboiler from one of the columns, providing potential capital and
energy cost savings (Long and Lee, 2014; Van Duc Longand Lee, 2013).
Luyben et al. (2004) has proposed a reactive distillation process for the enhanced production of n-butyl acetate with a
simpler process structure consisting of only three distillation columns that showed significant improvement in the
energy efficiency.
However, all of these configurations have similar drawbacks in that methyl acetate and methanol are recycled back to
the main reactive distillation column as azeotropes, which limits the reaction and energy efficiency of the reactive
distillation column.
Pervaporation (PV), or vapor permeation, of organic mixtures has been widely used in industry to overcome difficulties
with mixtures such as azeotropes or close-boiling mixtures (Kujawski, 2000; Naidu and Malik, 2011), and it is
considered to be a good technique for separating methanol from methyl acetate (Sain et al., 1998). Steinigeweg and
Gmehling (2004) and Svandov and Markos (2011) have reported experimental and simulation studies on the
integration of reactive distillation and pervaporation separation for n-butyl acetate production.
They proved that in order to increase the conversion of methyl acetate to n-butyl acetate, the recycle stream to the
reactive distillation column should be concentrated into pure methyl acetate.
Fig. Conventional reactive distillation process (RD + MC)for n-butyl acetate production.
Fig. Proposed system for thermally coupled reactive distillation with pervaporation (TCRD + PV).
Fig. Comparison of capital costs for different process Fig. Comparison of TACs for different process
configurations. configurations.
Between IPA and water, a homogeneous temperature minimum azeotrope exists with a water mole fraction of 0.3167
mol/mol and a boiling temperature of 80.4 at atmospheric pressure (1.013 bar) (Papa, et. al., 2010).
Fig. Process configuration, equipment dimensions and operating conditions of the optimized hybrid pervaporation-distillation
process.
In several cases, non-ideal aqueousorganic mixtures are formed which tend to form azeotropes. They can be
overcome using membrane separations like pervaporation and vapor permeation since they are very selective and not
limited by vaporliquid equilibrium (Rautenbach et. al., 1997).
In their work, the heterogeneously catalyzed esterification of propionic acid (ProAc) with 1-propanol (POH) to n-
propyl propionate (ProPro) and water (2 ) is investigated:
3 8 + 3 6 2 6 12 2 + 2
The esterification reaction is reversible; the equilibrium constant is a weak function of temperature.
The chemical system shows complex thermodynamic phase behavior with several binary and ternary azeotropes as
well as miscibility gaps.
Due to two binary homogeneous azeotropes (1-propanol water, propionic acidwater), one binary heterogeneous (n-
propyl propionatewater) as well as one ternary heterogeneous (n-propyl propionate1-propanolwater) temperature
minimum azeotrope, a conventional process requires a complex separation train downstream of the reactor.
Table Boiling points of pure components and azeotropic data at 1 atm (Buchaly et. al., 2007)
Fig. Influence of reboiler heat duty and reflux ratio, v, on product purity, xProPro,bottom (left) and propionic acid conversion,
XProAc (right).
It is not easy to carry out a direct comparison between VP and PV efficiency; however, VP, similar to gas separation,
could exhibit some advantages over PV. For example, the evaporation energy could be supplied in a separate
evaporator thus avoiding the use of heat exchangers. Then, a more favourable fluid dynamics allows the use of larger
modules with consequent benefits in terms of cost reduction. The processes which have been improved by integrating a
VP unit are mainly natural gas or organic solvents dehydration as well as water separation from air and its recovery
from the waste stream.
In a hybrid process, several possibilities exist to implement the PV or VP modules and the membrane separation
devices and the reactor can be separated into two units or integrated into a single one. For Example, Membrane
Reactor, Membrane distillation.
Fig. Direct Contact Membrane Distillation Fig. Sweeping Gas Membrane Distillation
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