DEPARTMENT OF CHEMICAL ENGINEERING KKEK 3221 CHEMICAL ENGINEERING REACTION II

Lecturer: Dr. Ngoh Gek Cheng

ASSIGNMENT 1

GROUP MEMBER: NAME 1. TAN AN MAY 2. TAN CHIU TENG MATRIC NUMBER KEK090050 KEK090051

Assignment 1 Q1) Properties of the catalyst.

KKEK 3221 Chemical Engineering Reaction II

Catalysts can increase the rates of both forward and reverse reaction, by providing an alternative path and lowering the activation energy, Ea of the reaction. It shortens the time needed to reach equilibrium. Catalysts do not change the extent of a reaction since they have no effect on the chemical equilibrium.

Figure 1: Potential energy diagram showing a reaction with catalyst has a lower Ea path. (Adapted from Wikipedia on 24 September 2011)

Catalysts can be regenerated and recovered unchanged in mass and chemical composition at the end of a reaction. Although catalyst not consumed by the reaction itself, they may be inhibited, deactivated, or destroyed by secondary processes. Each catalyst is specific to a certain reaction only. Catalyst can affect the selectivity of a reaction. Catalyst property might be affected by temperature and pressure. Catalysts are classified as positive and negative catalysts; positive catalysts speed the reaction whereas inhibitors (or negative catalysts) slow the reactions. There are homogeneous and heterogeneous catalysts; homogeneous catalysts function in the same phase as the reactants, it can be acids, bases and organometallic catalyst. Heterogeneous catalysts function in a different phase than the reactants, it can be solid powder and pellets.

Q2) The methods of manufacturing of catalyst. ( i.e. Precipitation & impregnation) Catalyst preparation involves 2 stages. First, rendering a metal-salty component into finely divided form on a support and secondly; conversion of the supported metal salt to a metallic or oxide state. The first stage is called dispersion and is achieved by impregnation, adsorption form solution, co-precipitation, or deposition, while the second stage is variously called calcination or reduction. It is brought about by a thermal treatment in either an inert atmosphere or an active atmosphere of either oxygen or hydrogen. When the active atmosphere is hydrogen the process is called reduction. Now, we will consider the preparation of supported catalyst by impregnation. Impregnation as a means of supported catalyst preparation is achieved by repeatedly dipping porous support into metal salt solution, such that the required weight of the active component is incorporated into the support without the use of excess of solution. This is then followed by drying and subsequent decomposition of the salt at an elevated temperature (about 400C), either by thermal decomposition or reduction. When used for the preparation of mixed metal 1

Assignment 1

KKEK 3221 Chemical Engineering Reaction II

catalyst, make sure that a component in an impregnating solution of metal salts is not selectively adsorbed, resulting in an unexpectedly different and undesirable concentration of metals in a mixed-metal catalyst. This technique has been widely used for the preparation of small amounts of catalyst for basic studies. Next, we will consider the preparation of supported catalyst by precipitation. The preparation of supported catalysts by the co-precipitation of metal ions with support ions usually produce an intimate mixing of catalyst and support. An example of this method is the co-precipitation of metal ions with aluminium ions to produce a precipitated alumina gel containing the metal hydroxide. This precipitate after calcined produces a refractory support with active component dispersed throughout the bulk as well as at the surface. However, in the preparation of multi-component catalysts, it is possible under improper conditions to obtain a heterogeneous product because of the different solubility products of the constituents. We can avoid this undesirable situation by appropriate forethought.

1. Impregnation It consists of repeated dipping of porous support pellets into a solution containing a desired catalytic agent. The agent must be applied uniformly in a predetermined quantity to a preset depth of penetration. This is especially true of catalysts based on noble metals. The liquid penetration into the pellets is hindered by air trapped in the pellet pores. Various techniques like pressurizing, vacuum treatment, acoustic activation etc. are used to facilitate the impregnation process. However, they are expensive and allow only limited control of absorption and penetration depth.

Precipitation

Q3) How catalyst can be deactivated and give detail on one type of catalyst deactivation. There are 4 main causes to deactivation of catalyst; fouling of the active surface with involatile reaction by-products, sintering or crystal growth of the active material, poisoning of the active surface by feed impurities, and blockage of the support pore structure. The activity of catalyst reduces gradually when the unwanted, harmful components of fuels and lubricants, or other impurities, are accumulated on the catalyst's surface and slowly poison the catalyst. Poisoning is defined as a loss of catalytic activity due to the chemisorption of impurities on the active sites. Poisons are substances that interact very strongly and irreversibly with the active sites. Poisoning is typically a slow phenomenon, but even the low levels of impurities are enough to cover the active sites and decrease the performance of a catalyst. The accumulation of poisons on the active sites blocks the access of reactants to these active sites. As a result of poisoning, the catalytic activity may be decreased without affecting the selectivity, but often selectivity is also changed since some of the active sites are deactivated while others are practically unaffected. Lead (Pb), sulfur (S), 2

Assignment 1

KKEK 3221 Chemical Engineering Reaction II

phosphorus (P), zinc (Zn), calcium (Ca), and magnesium (Mg) compounds are example of catalyst poisons. In addition, the best methods to reduce poisoning is to decrease the amount of poisons in the fuel and lubrication oils to more acceptable levels yet minimize the risk of deactivation of catalyst.

2.

Process that lead to the deactivation of catalyst are such as: Poisoning Sintering Aging

Poisoning Catalyst poisoning refers to the effect that a catalyst can be 'poisoned' if it reacts with another compound that bond chemically to its active surface sites. This effectively reduces the usefulness of the catalyst. Poisoned sites can no longer accelerate the reaction with which the catalyst was supposed to catalyze. An example can be seen with Raney nickel catalyst, which have reduced activity when it is in combination with mild steel. The loss in activity of catalyst can be overcome by having a lining of epoxy or other substances.

Assignment 1

KKEK 3221 Chemical Engineering Reaction II

Assignment 1

KKEK 3221 Chemical Engineering Reaction II