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Supplementary information for the course: Catalysis, Theory and Applications January 2002/ Paul C. J.

Kamer and Gadi Rothenberg


METHANOL SYNTHESIS

compiled by E. K. Poels and D. S. Brands

10.1 Introduction Catalytic processes for the synthesis of methanol have existed since the twenties. At first high pressure processes were used, which were introduced by BASF in 1923. The raw material for these processes, called synthesis gas, was a mixture of CO, H2 and frequently also CO2. The methanol synthesis reactions are highly exothermic: CO + 2H2 CO2 + 3H2 CH3OH CH3OH + H2O H298 = -90.8 kJ/mol H298 = -49.6 kJ/mol

The catalysts used were based on ZnO-Cr2O3 compounds and the process was operated at temperatures between 300 and 400C and at pressures between 250 and 350 bar. This is the well-known high pressure process. The zinc-chromite catalyst had a very high resistance to catalyst poisoning, especially towards sulphur, which was quite abundant in the early coal-based synthesis gases. Later, ICI developed the low pressure process, which was made possible by two developments which took place simultaneously. It had become possible to produce large amounts of pure synthesis gas, essentially free of poisons like sulphur and chlorine and a better catalyst was discovered: the combination Cu/ZnO which was clearly much more active. The problem with this Cu-catalyst was its sensitivity under process conditions. It became possible during the mid-sixties to produce a catalyst that was stable under process conditions by using support materials like Al2O3 and Cr2O3. With the low pressure process the synthesis takes place at pressures of 50-100 bar and temperatures of 220-280C. Modern methanol synthesis plants use a Cu/ZnO/Al2O3 catalyst. Reproducible preparation of this catalyst is very difficult, as the catalyst precursor must consist of several phases, of which the mixed metal hydroxycarbonates rosasite and hydrotalcite are the most important for achieving the desired activity and stability. A high catalyst activity is related to a high copper surface area or small crystallite size combined with intimate contact with the zinc promoter. The decrease in activity is connected with the loss of copper surface area by crystal growth, although the relationship is not unambiguous. The synthesis gas needed for the process can be prepared in several ways. In the past steam reforming of naphtha was frequently used. Another possibility was the partial oxidation of vacuum residues. Nowadays most synthesis gas is produced by reacting

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methane with steam. Natural gas and the gas which is released in oil production are particularly cheap raw materials. The synthesis gas is obtained by steam reforming (over a Ni/-Al2O3 catalyst at 1100 K): CH4 + H2O CO + 3 H2 Methanol is an important chemical with a world-wide production volume of some 14 million tons per annum. It is mainly used as a raw material for various chemical products, of which formaldehyde is the most important. Methanol is also frequently used in the production of energy carriers and additives for transportation fuel. One of the increasing uses for methanol is in the production of methyl tertiary butyl ether (MTBE) which is used to increase the octane number of lead free gasoline. A summary of the applications of methanol is given in table 10.1: Table 10.1: Applications of methanol ______________________________________________________________________ energetic (6%) non-energetic (94%) ______________________________________________________________________ - methanol additives in gasoline (1-2%) - formaldehyde (52%) - engine fuel (1%) - acetic acid (6%) - methyl tertiary butyl ether (MTBE)(4%) - dimethyl terephthalate(4%) - raw material for synthetic fuel - methyl halides (4%) - methyl amines (4%) - methyl methacrylate (4%) - solvent (8%) - others (8%) ______________________________________________________________________ 10.2 Mechanism The kinetics of the synthesis of methanol has been studied for a large range of catalysts, temperatures and pressures. An attempt has been made to clarify the mechanism by postulating a series of reaction steps (adsorption, reaction, desorption) from which a theoretical rate equation could be derived. Comparing the theoretical equation with experimental data would then given an experimental rate equation. The mechanisms deduced from these kinetic studies can be subdivided into three groups (see also fig. 10.1): I Carbon down hydrogenation in which first a formyl complex [HCO] is formed which is bonded to an M-site by the C-atom; II Oxygen down hydrogenation in which formate [HCOO-] is initially formed which is then bonded to an M-site by O; III Side on hydrogenation in which adsorbed formaldehyde [HCHO] is formed. The representation of the active site as "M" is a simplification as disagreement exists in literature concerning the nature and charge of the copper (or noble metal) species involved.

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Formyl and formate are found as intermediates in various investigations, whereas formaldehyde is only rarely identified. It is not simple to prove which mechanism is correct. Mixed reaction pathways have been suggested as well (see below). It is even possible that a generally valid mechanism does not exist.
I carbon down hydrogenation: O C M H formyl H C M O H H C M O H H H C M H H M + CH 3OH O H

II oxygen down hydrogenation: H OM CO formate H C O - O M 4H C H3 OM H2 III side on hydrogenation: O 2H C M O or C M H C H M formaldehyde O + H 2O H OM HM + CH OH 3 + CH3OH

2H

M + CH 3OH

Fig. 10.1:

Summary of proposed methanol synthesis mechanisms.

An attempt has been made to elucidate the mechanism for Rh/TiO2 by using a mixture of 13C16O and 12C18O. If methanol formation were to take place via dissociative adsorption then the isotope distribution in the product mixture would be: 13CH 16OH 3 13CH 18OH 3 12CH 18OH 3 12CH 18OH 3 25% 25% 25% 25%

If dissociation of CO does not take place and O-scrambling therefore also does not occur, the distribution would be: 13CH 16OH 3 12CH 18OH 3 50% 50%

As the latter is the case adsorption is non-dissociative, which is in agreement with the hypotheses of fig. 10.1.

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The oxygen down route is also incorrect because O-scrambling would then also occur. In the group:
H C O M

- O

the two O-atoms are equal and therefore it is unlikely that O-scrambling does not take place. This investigation was conducted with Rh-catalysts. It is not a priori certain that Cu or ZnO based catalysts would operate according to the same mechanism as noble metal catalysts do. Mechanism I is probably correct for the noble metal catalysts which form relatively strong metal-carbon bonds (Pt, Pd, Rh). In addition it is known from single crystal studies that CO adsorbs onto these metals with the carbon side towards the metal. On the other hand, from fundamental studies the most likely adsorption mode of CH3O- appears to be oxygen down. For this reason some authors suggest a transition from mechanism I to an oxygen down pathway at an intermediate stage. For ZnO and ZnO/Cr2O3 catalysts mechanism II is thought to be more likely. The large dipole moment and relatively irregular electron distribution of oxides make it more plausible for CO to adsorb via its O atom. The formate species has been identified during both methanol synthesis and decomposition over these catalysts. One of the important systems applied in industry, Cu/ZnO/Al2O3 is also thought to belong to this group. The group at ICI Katalco Research proposes a mechanism over Cu/ZnO/Al2O3 catalysts where CO2 is the predominant reagent in the synthesis gas. CO in their view only serves to keep the copper surface in the correct, reduced zerovalent state, forming CO2 in the process. Thus CO2 and H2 adsorb onto the Cu to form a formate species, which is progressively hydrogenated towards a methoxy-group and subsequently to methanol. This oxygen down type mechanism leaves little room for the promoting role of the ZnO, other than keeping the copper in a well-dispersed state. The current hypothesis of the ICI group seems to be that Zn exists as a Zn-H hydride under reaction conditions, somehow supplying hydrogen for the reaction by spill-over. Other possible structures for the active site include small epitaxial Cu clusters on top of the Cu-Zn-O mixed oxide; copper cations on a similar matrix; a dual Cu-Zn site. It seems the debate will continue for some time. 10.3 Commercial processes A scheme of the synthesis loop of the process is given in Fig. 10.2. Synthesis gas is mixed with recycled unreacted gas, pressurised in the compressor until the operational pressure is reached, then preheated in a heat exchanger until a

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temperature close to the reaction temperature is obtained and subsequently fed into the synthesis reactor. The formation of methanol is determined thermodynamically. Depending on the process conditions used, the product gas contains 4-8 vol-% methanol. A large part of the heat of condensation of methanol is transferred to the reactor feed in a feedeffluent heat-exchanger before the gas is cooled to room temperature in a water cooler. Approx. 95% of the methanol condenses here; separation of the gas phase takes place in a separator. After passing through the recycle compressor the gas is mixed with fresh synthesis gas and subsequently re-introduced into the reactor. A fixed percentage of the gas leaving the separator is continuously purged. This is to prevent inert gases that do not condensate (mainly N2 and CH4) from building up in the synthesis loop.
make-up syngas vent recycle compressor cold shot 220C heat exch.

separator CH3OH

condenser 270C reactor

to distillation

Fig. 10.2:

Scheme of a methanol synthesis loop.

The crude methanol is purified by means of distillation. In the topping column gases and impurities with a low boiling point are removed; a second refining column removes the heavier products and water. At present methanol is produced almost exclusively via three processes: the ICI, the Lurgi and the Mitsubishi processes. These processes differ mainly in their reactor designs and the way in which the produced heat is removed, see Fig. 10.3. The ICI design consists of a number of adiabatic catalytic beds, and cold gas is used to cool the reactant gases between the beds. This gives rise to temperature profiles in the reactor as illustrated in Fig. 10.4, in which also the concentration profile of the reactants and the products are indicated. The highest temperature is reached in the first catalyst bed. The Lurgi and Mitsubishi reactors have a much flatter temperature profile, as the reactor is almost isothermal owing to its cooling on the shell side by the generation of valuable high-pressure steam. As a result of the flat temperature profile, catalyst deactivation will be lower. However, in both processes the catalyst still deactivates, which means that the productivity decreases and the plant capacity is no longer met. Fortunately, the catalyst productivity is a function of the process

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pressure, so increasing the process pressure can compensate for the loss in activity. On doing so the plant can produce its design value over longer periods (2-3 years). Nowadays large methanol plants exclusively use centrifugal compressors to bring the synthesis gas to the desired operating pressure, which varies from 70 to 100 bar, depending on the activity of the catalyst, the lower pressure being used with fresh catalyst and the highest pressure at the end of the catalyst lifetime.
SYNGA SYNGA HIGH PRESSURE STEAM

COOLING WATER LURGI MITSUBISHI

ICI

Figure 10.3:

Some possible designs of a methanol synthesis reactor.

Figure 10.4:

Temperature, methanol and carbon monoxide/carbon dioxide profiles in an adiabatic reactor.

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