Semibatch process

Batch process Semibatch process Continuous process... 

Emulsion Process. The emulsion polymerization process utilizes water as a continuous phase with the reactants suspended as microscopic particles. This low viscosity system allows facile mixing and heat transfer for control purposes. An emulsifier is generally employed to stabilize the water insoluble monomers and other reactants, and to prevent reactor fouling. With SAN the system is composed of water, monomers, chain-transfer agents for molecular weight control, emulsifiers, and initiators. Both batch and semibatch processes are employed. Copolymerization is normally carried out at 60 to 100°C to conversions of - 97%. Lower temperature polymerization can be achieved with redox-initiator systems (51). 

Figure 2 shows a typical batch or semibatch emulsion process (52). A typical semibatch emulsion recipe is shown in Table 3 (53). 

Thermally activated initiators (qv) such as azobisisobutyroaittile (AIBN), ammonium persulfate, or benzoyl peroxide can be used in solution polymeriza tion, but these initiators (qv) are slow acting at temperatures required for textile-grade polymer processes. Half-hves for this type of initiator are in the range of 10—20 h at 50—60°C (13). Therefore, these initiators are used mainly in batch or semibatch processes where the reaction is carried out over an extended period of time. 

An example of a commercial semibatch polymerization process is the early Union Carbide process for Dynel, one of the first flame-retardant modacryhc fibers (23,24). Dynel, a staple fiber that was wet spun from acetone, was introduced in 1951. The polymer is made up of 40% acrylonitrile and 60% vinyl chloride. The reactivity ratios for this monomer pair are 3.7 and 0.074 for acrylonitrile and vinyl chloride in solution at 60°C. Thus acrylonitrile is much more reactive than vinyl chloride in this copolymerization. In addition, vinyl chloride is a strong chain-transfer agent. To make the Dynel composition of 60% vinyl chloride, the monomer composition must be maintained at 82% vinyl chloride. Since acrylonitrile is consumed much more rapidly than vinyl chloride, if no control is exercised over the monomer composition, the acrylonitrile content of the monomer decreases to approximately 1% after only 25% conversion. The low acrylonitrile content of the monomer required for this process introduces yet another problem. That is, with an acrylonitrile weight fraction of only 0.18 in the unreacted monomer mixture, the low concentration of acrylonitrile becomes a rate-limiting reaction step. Therefore, the overall rate of chain growth is low and under normal conditions, with chain transfer and radical recombination, the molecular weight of the polymer is very low. 

In the most common production method, the semibatch process, about 10% of the preemulsified monomer is added to the deionised water in the reactor. A shot of initiator is added to the reactor to create the seed. Some manufacturers use master batches of seed to avoid variation in this step. Having set the number of particles in the pot, the remaining monomer and, in some cases, additional initiator are added over time. Typical feed times ate 1—4 h. Lengthening the feeds tempers heat generation and provides for uniform comonomer sequence distributions (67). Sometimes skewed monomer feeds are used to offset differences in monomer reactivity ratios. In some cases a second monomer charge is made to produce core—shell latices. At the end of the process pH adjustments are often made. The product is then pumped to a prefilter tank, filtered, and pumped to a post-filter tank where additional processing can occur. When the feed rate of monomer during semibatch production is very low, the reactor is said to be monomer starved. Under these... 

The batch process is similar to the semibatch process except that most or all of the ingredients are added at the beginning of the reaction. Heat generation during a pure batch process makes reactor temperature control difficult, especially for high soHds latices. Seed, usually at 5—10% soHds, is routinely made via a batch process to produce a uniform particle-size distribution. Most kinetic studies and models are based on batch processes (69). 

These mixing systems offer high flexibility because they can be operated in batch, semibatch, or continuous modes. Adequate mixing is a prerequisite for the success of chemical processes in terms of rninirnizing investment and operating costs. In addition, chemical reactions with... 

Specific reactor characteristics depend on the particular use of the reactor as a laboratory, pilot plant, or industrial unit. AH reactors have in common selected characteristics of four basic reactor types the weH-stirred batch reactor, the semibatch reactor, the continuous-flow stirred-tank reactor, and the tubular reactor (Fig. 1). A reactor may be represented by or modeled after one or a combination of these. SuitabHity of a model depends on the extent to which the impacts of the reactions, and thermal and transport processes, are predicted for conditions outside of the database used in developing the model (1-4). 

When surfactant-coated glass fibers are included to improve product flexibility and reduce thermal expansion, these semibatch processes are termed reinforced reaction injection mol ding (RRIM). 

The aqueous emulsion polymerization can be conducted by a batch, semibatch, or continuous process (Fig. 5). In a simple batch process, all the ingredients are charged to the reactor, the temperature is raised, and the polymerization is mn to completion. In a semibatch process, all ingredients are charged except the monomers. The monomers are then added continuously to maintain a constant pressure. Once the desired soflds level of the latex is reached (typically 20—40% soflds) the monomer stream is halted, excess monomer is recovered and the latex is isolated. In a continuous process (37), feeding of the ingredients and removal of the polymer latex is continuous through a pressure control or rehef valve. 

Except in the laboratoiy, batch reactors are mostly liquid phase. In semibatch operation, a gas of limited solubility may be fed in gradually as it is used up. Batch reaclors are popular in practice because of their flexibility with respect to reaction time and to the lands and quantities of reactions that they can process. 

Example 11 Balances of a Semibatch Process The reaction A -l-B Products is carried out by first charging B into the vessel to a concentration Cfco and a volume V,o, then feeding a solution of concentration C o at volumetric rate V for a time t. 

In order to account for both micromixing and mesomixing effects, a mixing model for precipitation based on the SFM has been developed and applied to continuous and semibatch precipitation. Establishing a network of ideally macromixed reactors if macromixing plays a dominant role can extend the model. The methodology of how to scale up a precipitation process is depicted in Figure 8.8. 

Zauner, R. and Jones, A.G., 2000b. Scale-up of continuous and semibatch precipitation processes. Industrial and Engineering Chemistry Research, 39, 2392-2403. 

All processes may be classified as batch, continuous, or semibatch depending on how materials are transferred into and out of the system. Also, the process operation may be characterized as unsteady state (i.e., transient) or steady state, depending on whether the process variables (e.g., pressure, temperature, compositions, flowrate, etc.) are changing with time or not, respectively. In a batch process, the entire feed material (i.e., charge) is added instantaneously to the system marking the beginning of the process, and all the contents of the system including the products are removed at a later time, at the end of the process. In a continuous process, the materials enter and leave the system as continuous streams, but not necessarily at the same rate. In a semibalch process, the feed may be added at once but the products removed continuously, or vice versa. It is evident that batch and semibatch processes are inherently unsteady state, whereas continuous processes may be operated in a steady or unsteady-state mode. Start-up and shut-down procedures of a steady continuous production process are examples of transient operation. 

Differential and Integral Balances. Two types of material balances, differential and integral, are applied in analyzing chemical processes. The differential mass balance is valid at any instant in time, with each term representing a rate (i.e., mass per unit time). A general differential material balance may be written on any material involved in any transient process, including semibatch and unsteady-state continuous flow processes ... 

Gas phase olefin polymerizations are becoming important as manufacturing processes for high density polyethylene (HOPE) and polypropylene (PP). An understanding of the kinetics of these gas-powder polymerization reactions using a highly active TiCi s catalyst is vital to the careful operation of these processes. Well-proven models for both the hexane slurry process and the bulk process have been published. This article describes an extension of these models to gas phase polymerization in semibatch and continuous backmix reactors. 

The yield that can be attained by a semibatch process is generally higher because the semibatch run starts from scratch, with maximum values of both variables Cg (o) = Cg and k] (o) = k . However, the yield from a continuous run in which t equals the batch time is governed by the product of Cg (t) and kj (t), so > and k (t) = k °. Because neither of these conditions is likely to be fulfilled completely, a continuous polymerization in a backmix reactor will probably always fail to attain the Y attainable by a semibatch reactor at the same t. However, several backmix reactors in series will approach the behavior of a plug flow continuous reactor, which is equivalent to a semibatch reactor. 

This section is divided into three parts. The first is a comparison between the experimental data reported by Wisseroth (].)for semibatch polymerization and the calculations of the kinetic model GASPP. The comparisons are largely graphical, with data shown as point symbols and model calculations as solid curves. The second part is a comparison between some semibatch reactor results and the calculations of the continuous model C0NGAS. Finally, the third part discusses the effects of certain important process variables on catalyst yields and production rates, based on the models. 

The performance of a novel microwave-induced pyrolysis process was evaluated by studying the degradation of HDPE and aluminiutn/polymer laminates in a semibatch bench-scale apparatus. The relationship between temperature, residence time of the pyrolytic products in the reactor, and the chemical composition of the hydrocarbon fraction produced was investigated. 28 refs. 

The SimuSolv program (Program B) which was written to simulate the reaction finishing process with extra initiator addition is similar to Program A and uses the monomer and initiators mass balance equations with optimized values of the kinetic parameters. The semibatch step had been experimentally optimized for obtaining... 

Therefore, many traditional designs, such as stirred tank reactors, incorporate heat transfer in the process (jacket, external or internal coil, etc.). However, in these devices, there is a significant distance between the heat transfer site and the site of the chemical reaction where heat is released. As a consequence semibatch mode is implemented while batch mode and/or systems are diluted. 

As expected, heat exchanged per unit of volume in the Shimtec reactor is better than the one in batch reactors (15-200 times higher) and operation periods are much smaller than in a semibatch reactor. These characteristics allow the implementation of exo- or endothermic reactions at extreme operating temperatures or concentrations while reducing needs in purifying and separating processes and thus in raw materials. Indeed, since supply or removal of heat is enhanced, semibatch mode or dilutions become useless and therefore, there is an increase in selectivity and yield. 

From the process safety point of view, the evaluation of the intrinsic safe character of HEX compared to batch or semibatch reactors has been investigated [33, 37]. Two points clearly show the interest in the HEX reactors ... 

To illustrate the complexity of process optimization, suppose that we are to scale-up a semibatch stirred-tank reactor for carrying out the following consecutive reactions ... 

In order to illustrate how the mode of operation can positively modify selectivity for a large reactor of poor heat-transfer characteristics, simulations of the reactions specified in Example 5.3.1.4 carried out in a semibatch reactor were performed. The reaction data and process conditions are essentially the same as those for the batch reactor, except that the initial concentration of A was decreased to cao = 0.46 mol litre, and the remaining amount of A is dosed (1) either for the whole reaction time of 1.5 h with a rate of 0.1 mol m s", or (2) starting after 0.5 h with a rate of 0.15 mol m " s". It is assumed that the volume of the reaction mixture and its physical properties do not change during dosing. The results of these simulations are shown in Fig. 5.3-15. The results of calculation for reactors of both types are summarized in Table 5.3-3. 

Column reactors can contain a draft tube - possibly filled with a packing characterized by low pressure drop - or be coupled with a loop tube, to make the gas recirculating within the reaction zone (see Fig. 5.4-9). In recent years, the Buss loop reactor has found many applications in two- and three-phase processes About 200 Buss loop systems are now in operation worldwide, also in fine chemicals plants. This is due to the high mass-transfer rate between the gas and the liquid phase. The Buss loop reactor can be operated semibatch-wise or continuously. As a semibach reactor it is mostly used for catalytic hydrogenations. 

Semibatch reactors are often used to mn highly exothermic reactions isothermally, to run gas-liquid(-solid) processes isobarically, and to prevent dangerous accumulation of some reactants in the reaction mixture. Contrary to batch of)eration, temperature and pressure in semibatch reactors can be varied independently. The liquid reaction mixture can be considered as ideally mixed, while it is assumed that the introduced gas flows up like a piston (certainly this is not entirely true). Kinetic modelling of semibatch experiments is as difficult as that of batch, non-isotherma experiments. 

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