HYDROGENATION OF ETHYLENE ON CU CATALYST

Ethylene, also called ethene, is one of the most useful of all chemical intermediates. It is made of two carbon atoms linked together by a double bond. This bond is very strong, but it also reactive and it is possible to form a range of other useful compounds by adding groups across it. Reaction with water, for example, converts ethylene to ethanol, while reaction with hydrogen converts ethylene into ethane.

Ethylene is part of the hydrocarbon group of organic compounds, so called because they are made up of just hydrogen and carbon. The principle source of hydrocarbons is crude oil, which comprises a range of hydrocarbons from the light compounds such as methane, ethane and ethylene up to heavy, long-chain carbon compounds such as asphalt and bitumen. Although ethylene occurs in crude oil, most of it is produced by splitting up the long chain compounds using a process called cracking. Both ethylene and hydrogen exist at room temperature as gases, however nothing happens when these two gases are mixed. However, the addition of a catalyst leads to the rapid hydrogenation of the ethylene to form ethane in a process called catalytic hydrogenation. Effective catalysts for this process include platinum, palladium and nickel. These metals are often supported on activated charcoal. Catalytic hydrogenation is an example of heterogeneous catalysis, as the reactants and the catalyst are in different phases. The only use of ethylene hydrogen is in the production of ethane, however many other useful products can be synthesized by reacting different compounds with ethylene. Unsupported reduced copper is usually not active as a hydrogenation catalyst and tends to lose its activity at high temperatures. Copper catalysts are known to be highly selective, as in partial hydrogenation of polynuclear aromatic compounds such as anthracene and phenanthrene. Industrially it is an important component in the catalysts for methanol synthesis in lowering the operation temperature and pressure. The catalyst has been shown to be particularly effective for the hydrogenation of carboxylic esters to alcohols. Relatively low activity of copper catalysts for carboncarbon double bonds over carbonyl functions has been applied to selective hydrogenation of unsaturated aldehydes to unsaturated alcohols.

Cu catalyst is a heterogeneous catalyst. The catalyst is the principle of LangmuirHinshelwood mechanism. This mechanism is based on the following assumption: both reaction partners are adsorbed without dissociation at different free sites on the catalyst surface. This is then followed by the actual surface reaction between neighboring chemisorbed molecules to give the product C, adsorbed on the surface. In the final step the product is desorbed. The reaction sequence is thus:

The LangmuirHinshelwood mechanism can be depicted as :

Each of the above-mentioned steps can be rate determining, but here we shall only discuss the case in which the surface reaction between the two adsorbed molecules is the rate-determining

step. On the basis of the relationship for mixed adsorption, the following rate equation can be formulated :

Of the numerous boundary conditions that are possible, we will consider only two in more detail here: 1) When both starting materials are only weakly adsorbed, then both KA and KB<=1 and the rate equation becomes reff = kpA pB and k_ = kKAKB. The reaction is first order in both reactants and second order overall. 2) When A is weakly and B strongly adsorbed, KA <=1<=KB and the rate equation reduces to

Catalysts have only a limited lifetime. Some lose their activity after a few minutes, others last for more than ten years. The maintenance of catalyst activity for as long as possible is of major economic importance in industry. A decline in activity during the process can be the result of various physical and chemical factors, for example: Blocking of the catalytically active sites Loss of catalytically active sites due to chemical, thermal, or mechanical processes

Reaction

Hydrogenation of ethylene on Cu catalysts C2H4 + H2_C2H6 200300 0C 50100 bar

Reaction Conditions

: :

Catalyst Catalyst lifetime [years]

: :

Cu 28

Deactivation : process

slow sintering

The four most common causes of catalyst deactivation are: Poisoning of the catalyst. Typical catalyst poisons are H2S, Pb, Hg, S, P Deposits on the catalyst surface block the active centers and change the pore structure (e. g., coking) Thermal processes and sintering of the catalyst lead to a loss of active surface area Catalyst losses by evaporation of components (e. g., formation of volatile metal carbonyls with CO)

Metal catalysts are highly sensitive to small amounts of certain impurities in the reaction medium. Catalytically active metals make their d orbitals available for adsorption, and this is the key to understanding both their catalytic activity and their sensitivity to poisons. Poisons for metals can be classified in three groups: Nonmetallic ions Metal ions Unsaturated molecules The mechanism of deactivation of Cu/Zn catalyst poisoned by organic chlorides in hydrogenation of methyl laurate to lauryl alcohol in a slurry phase was studied in a stirred autoclave. The catalyst was prepared by co-precipitation, and the un-poisoned and poisoned catalysts were characterized using XRD, BET, ICP-AES and SEM, respectively. The results indicated that both of catalytic activity and selectivity decreased with increasing amount of chlorides in methyl laurate. According to the characterization of the catalysts, the main causes for the chlorine deactivation of the Cu/Zn catalyst were that the chlorides could modify the valence state of active sites, decrease the BET surface area, and promote the growth of crystal and catalyst agglomeration. Further investigation indicated that chlorine atom decomposed from the chlorides combined with ZnO to produce ZnCl2, which could be dissolved in the liquid and promote ester-exchange reaction to lauryl laurate as Lewis acid.

Promoters are substances that are themselves not catalytically active but increase the activity of catalysts. The function of these substances, which are added to catalysts in amounts of a few per cent, has not been fully elucidated. There are four types of promoters: - Structure promoters increase the selectivity by influencing the catalyst surface such that the number of possible reactions for the adsorbed molecules decreases and a favored reaction path dominates. They are of major importance since they are directly involved in the solid-state reaction of the catalytically active metal surface. - Electronic promoters become dispersed in the active phase and influence its electronic character and therefore the chemical binding of the adsorbate. Textural promoters inhibit the growth of catalyst particles to form larger, less active

structures during the reaction. Thus they prevent loss of active surface by sintering and increase the thermal stability of the catalyst. - Catalyst-poison-resistant promoters protect the active phase against poisoning by impurities, either present in the starting materials or formed in side reactions.

A catalyst may contain one active component and one or more promoters. The fraction of active components usually exceeds 75 %. Since the above four effects tend to overlap in practice, it is sometimes difficult to precisely define the function of a promoter. Promoters are the subject of great interest in catalyst research due to their remarkable influence on the activity, selectivity, and stability of industrial catalysts. Many promoters are discovered serendipitously; few are the result of systematic research. This sector of catalyst research is often the scene of surprising discoveries.

Catalyst (use) Promoters Function

: Cu/ZnO/Al2O3 (low-temperature conversion) : ZnO : decreased Cu sintering

Catalyst Test Reactors and Kinetic Modeling Reaction Conditions: 12 g Cu catalyst, cylindrical pellets,

diameter = height = 5 mm 2252650C, 2080 bar; Feed stream 725 % CO 115 % CO2 6090 % H2 Throughput 0.21.2 m3/h Recycle ratio R>=30 rCH3OH = 0.010.09 kmol (kg cat.)_1h_1 LangmuirHinshelwood kinetics were determined, and the rate-determining step is reduction of the intermediate formaldehyde :

Jet loop reactor for catalyst investigations (high-pressure laboratory, FH Mannheim, Germany) 1) Thermal mass flow controller (up to 200 bar); 2) Nozzle, interchangeable; 3) Catalyst pellets on wire mesh; 4) Central tube; 5) Heating band 500 W; 6) Microfilter; 7) Precision feed valve; 8) Supplementary heating; 9) Gas meter

Numerous kinetic studies with such reactors have been reported in the literature, including:

 Hydrodesulfurization of model substances such as dibenzothiophene Hydrogenation of olefins Dehydrocyclization reactions The fewest experimental problems are caused by the integral reactor due to its simple construction and straightforward operation. It consists of a flow tube, 2050 cm in length and ca. 2 cm in diameter, filled with catalyst. The conversion achieved in such reactors is high and can readily be determined by comparing the initial and final concentrations of a reactant. A test series is carried out with variation of the values of the catalyst mass mcat. or the feed flow rate nA,0, thus covering a wide range of conversions. The favored method is to evaluate the data with a differential form of the design equation of the tubular reactor

The rate rA can be obtained directly from the individual measurements by graphical differentiation. The slope of the tangent of the conversiontime factor curve corresponds to the momentary reaction rate under the given test conditions. The disadvantage of the integral reactor is that it can not be operated isothermally and that the measured overall conversion is generally the result of a complex interplay between transport phenomena and chemical reaction. Hence the integral reactor is mainly used for comparitive catalyst studies and lifetime tests. Its advantages are: Rapid, empirical, and practice-relevant process development Conclusions about catalyst activity from changes in temperature and concentration profiles Catalyst deactivation can be followed Relatively simple scale-up