Waste Minimisation in Reactors The reactor is the heart of the process and can be a primary source of waste products.

Under normal operating conditions there are five major sources of waste from reactions. (a) Low conversion if recycling is difficult If it is not possible to recycle unreacted feed material back to the reactor inlet then low conversion in the reactor will lead to waste of that unreacted feed. Waste by-products from the primary reactions The primary reaction can produce waste by-products, e.g. Feed 1 + Feed 2 product + waste by-product Waste by-products from secondary reactions Secondary reactions can produce waste by-products, e.g. Feed 1 + Feed 2 product waste by-product Feed impurities undergo reaction Impurities in the feed materials can react to produce additional waste by-products. Catalyst waste Catalyst is either degraded and requires changing or is lost and cannot be recycled.

(b)

(c)

(d)

(e)

(a)

Low conversion if recycling is difficult If recycling is not possible we should, in general, try to achieve a high conversion in the reactor. If the reaction system involves a single, irreversible reaction then a higher conversion can be achieved using longer residence time, higher temperature or higher pressure. The problem of forcing a high conversion with single reactions becomes acute if the difficulty of separation and recycling coincides with the reaction being reversible. There is a maximum conversion, the equilibrium conversion, which we cannot exceed even with long residence time. What can we do to force a higher conversion for reversible reaction? We have a number of options available to shift the equilibrium and therefore force a higher conversion. We can change: (a) the feed ratio, e.g. use an excess of one reactant; (b) inert concentration, e.g. add inert material if reaction leads to increased number of moles; (c) temperature, e.g. raise temperature for enothermic reactions; (d) pressure, e.g. increase the pressure if reaction leads to a decrease in the number of moles. Alternatively, intermediate separation of products as the reaction proceeds can be an effective means of forcing higher conversion. A common example of this technique is in the manufacture of sulphuric acid where, to force a higher conversion of SO2 to SO3, the product gases undergo

reaction followed by a first stage absorption to remove SO3. The remaining product gases then pass through a final reaction stage. By this means, conversion of SO2 to SO3 is increased from typically 97% to over 99% with a corresponding reduction in SO2 emissions. (b) Waste by-products from the primary reactions If the reaction is of the form: Feed 1 + Feed 2 product + waste by-product then we can usually only avoid the formation of waste by using a different reaction path. This will likely involve a change in feed stock, different reaction chemistry and possibly a totally different process. (c) Waste by-products from secondary reactions A typical example of this situation is in the following reaction system: Feed 1 + Feed 2 product waste by-product However, there are many classes of multiple reactions. The action necessary to minimise reactor waste depends on the class of the reaction system. (d) Feed impurities undergo reaction If one or more feeds to the reactor contains an impurity, this impurity can become waste, or even worse, could react to produce waste by-products. Clearly, the best solution to feed impurities is feed purification. However, the decision as to whether to purify the feed or purify the product should be taken bearing in mind all associated costs, i.e. raw materials, feed purification and waste treatment. (e) Catalyst waste We can reduce waste from catalysts by using heterogeneous catalysts rather than homogeneous catalysts, which are often difficult to separate and recycle. In addition, we should look to prolong catalyst life which can be done by avoiding local extreme conditions. In general, a number of actions can be taken to help to improve reactions and reduce waste, these include: (its true for both catalysts and feed) (1) Better flow distribution The quality of mixing in a reactor is crucial and here is an area that deserves more attention than it typically gets. The problem is illustrated in Figure1. Reactants entering at the top of a fixed catalyst bed are poorly distributed. Part of the feed is short-circuits down through the centre of the reactor and does not allow adequate time for conversion to desired products. In contrast, feed that is closer to the walls remains in the reactor too long and overreacts to byproducts that eventually become waste. One solution is to add some sort of distributor at the reactor inlet that causes the feed to move uniformly through all parts of the reactor. A special collector at the bottom of the reactor may also be necessary to prevent the flow from necking down the outlet. Similarly, if a gas reactant is added to a liquid, the gas needs to be finely dispersed and evenly distributed throughout the liquid phase.

(2)

Improve catalyst Because of the significant effect a catalyst has on reactor conversion and product mix, searching for better catalysts should be an on-going activity. Changes in the chemical make over of a catalyst, the method by which it is prepared, or its physical characterisation (size, shape, porosity, etc.) can lead to substantial improvements in catalyst life and effectiveness. (3) Improve physical mixing in the reactor Modifications to the reactor such as adding or improving baffles, installing a higher rpm motor on the agitator(s) or using a different mixer blade design (or multiple impellers) can improve mixing. Pumped recirculation can be added or increased. Two fluids going through a pump, however, do not necessarily mix well and a static mixer may be needed to ensure good contacting. (4) Improve way in which reactants are added The idea here is to get closer to ideal reactant concentrations before the feed enters the reactor. This helps avoid secondary reactions which form unwanted by-products. The way NOT to add reactants is shown in the upper half of Figure 2. It is doubtful that the ideal concentration exists anywhere in this reactor. A consumable catalyst, especially, should be diluted in one of the feed streams (one which does not react in the presence of the catalyst). Part 2 of the figure illustrates one approach to improving the situation by improving mixing using three in-line static mixtures. (5) Consider different reactor design The classic stirred-tank back mix reactor is not necessarily the best choice. A plug flow reactor offers the advantage that it can be staged and each stage can be run at different conditions (especially temperature), closely controlling the reaction for optimum product mix and minimum waste. (6) Provide separate reactor for recycle streams Recycling by-product and waste streams is an excellent technique for reducing waste, but often the ideal reactor conditions for converting recycle streams back to useable products are considerably different from conditions in the primary reactors. One solution is to provide a separate, smaller reactor for handling recycle and waste streams as illustrated in Figure 3. Temperature, pressure and concentrations can then be optimised in both reactors to take maximum advantage of reaction kinetics. (7) Improve control For a given reactor configuration, there is one set of operating conditions that is optimum at any given time. The control system should know that condition and make it occur, with little fluctuation. Such control may be complex, particularly in the case of batch reactor operation which frequently reduces the formation of waste products. Advanced computer control systems are capable of responding to process upsets and product changes swiftly and smoothly, producing a minimum of unwanted by-products. (8) Examine heating and/or cooling techniques

The technique for heating or cooling the reactor needs to be examined, especially to avoid hot-spots or overheated fee