1) Carbon tetrachloride is used to produce chlorofluorocarbons through reactions with hydrogen fluoride and a catalyst. These compounds deplete the ozone layer and their production is being reduced.
2) Synthesis gas is produced through steam reforming of natural gas. Natural gas is treated and reacted with steam over a catalyst at high temperatures and pressures to produce a mixture of hydrogen, carbon monoxide, and other gases.
3) The synthesis gas is further treated through secondary reforming, shift conversion, and methanation to remove impurities like carbon monoxide and produce a hydrogen-rich gas for ammonia synthesis.
1) Carbon tetrachloride is used to produce chlorofluorocarbons through reactions with hydrogen fluoride and a catalyst. These compounds deplete the ozone layer and their production is being reduced.
2) Synthesis gas is produced through steam reforming of natural gas. Natural gas is treated and reacted with steam over a catalyst at high temperatures and pressures to produce a mixture of hydrogen, carbon monoxide, and other gases.
3) The synthesis gas is further treated through secondary reforming, shift conversion, and methanation to remove impurities like carbon monoxide and produce a hydrogen-rich gas for ammonia synthesis.
1) Carbon tetrachloride is used to produce chlorofluorocarbons through reactions with hydrogen fluoride and a catalyst. These compounds deplete the ozone layer and their production is being reduced.
2) Synthesis gas is produced through steam reforming of natural gas. Natural gas is treated and reacted with steam over a catalyst at high temperatures and pressures to produce a mixture of hydrogen, carbon monoxide, and other gases.
3) The synthesis gas is further treated through secondary reforming, shift conversion, and methanation to remove impurities like carbon monoxide and produce a hydrogen-rich gas for ammonia synthesis.
1) Carbon tetrachloride is used to produce chlorofluorocarbons through reactions with hydrogen fluoride and a catalyst. These compounds deplete the ozone layer and their production is being reduced.
2) Synthesis gas is produced through steam reforming of natural gas. Natural gas is treated and reacted with steam over a catalyst at high temperatures and pressures to produce a mixture of hydrogen, carbon monoxide, and other gases.
3) The synthesis gas is further treated through secondary reforming, shift conversion, and methanation to remove impurities like carbon monoxide and produce a hydrogen-rich gas for ammonia synthesis.
Carbon tetrachloride is used to produce chlorofluorocarbons by the
reaction with hydrogen fluoride using an antimony pentachloride (SbCl5) catalyst:
CCl4 + HF r CCl3F + HCl
CCl4 + 2HF r CCl2F2 + 2HCl
The formed mixture is composed of trichlorofluoromethane (Freon-11)
and dichlorodifluoromethane (Freon-12). These compounds are used as aerosols and as refrigerants. Due to the depleting effect of chlorofluoro- carbons (CFCs) on the ozone layer, the production of these compounds may be reduced appreciably. Much research is being conducted to find alternatives to CFCs with lit- tle or no effect on the ozone layer. Among these are HCFC-123 (HCCl2CF3) to replace Freon-11 and HCFC-22 (CHClF2) to replace Freon-12 in such uses as air conditioning, refrigeration, aerosol, and foam. These compounds have a much lower ozone depletion value com- pared to Freon-11, which was assigned a value of 1. Ozone depletion values for HCFC-123 and HCFC-22 relative to Freon-11 equals 0.02 and 0.055, respectively.4
SYNTHESIS GAS (STEAM REFORMING OF NATURAL GAS)
As mentioned in Chapter 4, synthesis gas may be produced from a vari-
ety of feedstocks. Natural gas is the preferred feedstock when it is avail- able from gas fields (nonassociated gas) or from oil wells (associated gas). The first step in the production of synthesis gas is to treat natural gas to remove hydrogen sulfide. The purified gas is then mixed with steam and introduced to the first reactor (primary reformer). The reactor is con- structed from vertical stainless steel tubes lined in a refractory furnace. The steam to natural gas ratio varies from 4–5 depending on natural gas composition (natural gas may contain ethane and heavier hydrocarbons) and the pressure used. A promoted nickel type catalyst contained in the reactor tubes is used at temperature and pressure ranges of 700–800°C and 30–50 atmos- pheres, respectively. The reforming reaction is equilibrium limited. It is favored at high temperatures, low pressures, and a high steam to carbon ratio. These conditions minimize methane slip at the reformer outlet and yield an equilibrium mixture that is rich in hydrogen.5 Chapter 5 1/22/01 11:01 AM Page 141
Chemicals Based on Methane 141
The product gas from the primary reformer is a mixture of H2, CO, CO2, unreacted CH4, and steam. The main steam reforming reactions are:
For the production of methanol, this mixture could be used directly with no further treatment except adjusting the H2/(CO + CO2) ratio to approx- imately 2:1. For producing hydrogen for ammonia synthesis, however, further treatment steps are needed. First, the required amount of nitrogen for ammonia must be obtained from atmospheric air. This is done by par- tially oxidizing unreacted methane in the exit gas mixture from the first reactor in another reactor (secondary reforming). The main reaction occurring in the secondary reformer is the partial oxi- dation of methane with a limited amount of air. The product is a mixture of hydrogen, carbon dioxide, carbon monoxide, plus nitrogen, which does not react under these conditions. The reaction is represented as follows:
CH4 + 1/2 (O2 + 3.76 N2) r CO + 2H2 + 1.88 N2 ∆H° = –32.1 KJ
The reactor temperature can reach over 900°C in the secondary reformer due to the exothermic reaction heat. Typical analysis of the exit gas from the primary and the secondary reformers is shown in Table 5-1. The second step after secondary reforming is removing carbon monoxide, which poisons the catalyst used for ammonia synthesis. This is done in three further steps, shift conversion, carbon dioxide removal, and methanation of the remaining CO and CO2.
Table 5-1 Typical analysis of effluent from primary and secondary reformers Constituent Primary reformer Secondary reformer H2 47 39.0 CO 10.2 12.2 CO2 6.3 4.2 CH4 7.0 0.6 H2O 29.4 27.0 N2 0.02 17.0 Chapter 5 1/22/01 11:01 AM Page 142
142 Chemistry of Petrochemical Processes
Shift Conversion
The product gas mixture from the secondary reformer is cooled then subjected to shift conversion. In the shift converter, carbon monoxide is reacted with steam to give carbon dioxide and hydrogen. The reaction is exothermic and independ- ent of pressure:
CO(g) + H2O (g) r CO2(g) + H2(g) ∆H° = –41 KJ
The feed to the shift converter contains large amounts of carbon
monoxide which should be oxidized. An iron catalyst promoted with chromium oxide is used at a temperature range of 425–500°C to enhance the oxidation. Exit gases from the shift conversion are treated to remove carbon dioxide. This may be done by absorbing carbon dioxide in a physical or chemical absorption solvent or by adsorbing it using a special type of molecular sieves. Carbon dioxide, recovered from the treatment agent as a byproduct, is mainly used with ammonia to produce urea. The product is a pure hydrogen gas containing small amounts of carbon monoxide and carbon dioxide, which are further removed by methanation.
Methanation
Catalytic methanation is the reverse of the steam reforming reaction.
Hydrogen reacts with carbon monoxide and carbon dioxide, converting them to methane. Methanation reactions are exothermic, and methane yield is favored at lower temperatures:
3H2(g) + CO(g) r CH4(g) + H2O(g) ∆H° = –206 KJ
4H2(g) + CO2 (g) r CH4(g) + 2H2O(g) ∆H° = –164.8 KJ
The forward reactions are also favored at higher pressures. However, the space velocity becomes high with increased pressures, and contact time becomes shorter, decreasing the yield. The actual process conditions of pressure, temperature, and space velocity are practically a compromise of several factors. Rany nickel is the preferred catalyst. Typical methanation reactor operating conditions are 200–300°C and approximately 10 atmospheres. The product is a gas mixture of hydrogen and nitrogen hav- ing an approximate ratio of 3:1 for ammonia production. Figure 5-2 Chapter 5 1/22/01 11:01 AM Page 143
Chemicals Based on Methane 143
Figure 5-2. The ICI process for producing synthesis gas and ammonia:6 (1) desul- furization, (2) feed gas saturator, (3) primary reformer, (4) secondary reformer, (5) shift converter, (6) methanator, (7) ammonia reactor.
shows the ICI process for the production of synthesis gas for the manu- facture of ammonia.6
CHEMICALS BASED ON SYNTHESIS GAS
Many chemicals are produced from synthesis gas. This is a conse-
quence of the high reactivity associated with hydrogen and carbon monoxide gases, the two constituents of synthesis gas. The reactivity of this mixture was demonstrated during World War II, when it was used to produce alternative hydrocarbon fuels using Fischer Tropsch technology. The synthesis gas mixture was produced then by gasifying coal. Fischer Tropsch synthesis of hydrocarbons is discussed in Chapter 4. Synthesis gas is also an important building block for aldehydes from olefins. The catalytic hydroformylation reaction (Oxo reaction) is used with many olefins to produce aldehydes and alcohols of commercial importance. The two major chemicals based on synthesis gas are ammonia and methanol. Each compound is a precursor for many other chemicals. From ammonia, urea, nitric acid, hydrazine, acrylonitrile, methylamines and many other minor chemicals are produced (see Figure 5-1). Each of these chemicals is also a precursor of more chemicals. Methanol, the second major product from synthesis gas, is a unique compound of high chemical reactivity as well as good fuel properties. It
