Primary shift

Tile partially purilied synthesis gas leaves the C02 absorber containing approximately 0.1% CO2 and 0.5% CO. This gas is preheated at the methanator inlet by heat exchange with the synthesis-gas compressor interstage cooler and the primary-shift converter effluent and reacted over a nickel oxide catalyst bed in the methanator. The methanation reactions are highly exothermic and are equilibrium favored by low temperatures and high pressures. 

The primary shifts vary widely with different nuclei of different groups and are sensitive to the ionization state of the molecnle. 

It should be mentioned that so-called secondary shifts can be of importance, particularly when working at high resolution and using monochroiiiated radiation. All the chemical shifts discussed so far have been primary shifts. That is. (he binding energy for the core level of the atom in the particular electronic en-... 

Hydnde shifts often occur during the dehydration of primary alcohols Thus although 1 butene would be expected to be the only alkene formed on dehydration of 1 butanol It IS m fact only a minor product The major product is a mixture of cis and trans 2 butene... 

A mechanism for the formation of these three alkenes is shown m Figure 5 9 Dissociation of the primary alkyloxonmm ion is accompanied by a shift of hydride from C 2 to C 1 This avoids the formation of a primary carbocation leading instead to a sec ondary carbocation m which the positive charge is at C 2 Deprotonation of this carbo cation yields the observed products (Some 1 butene may also arise directly from the pri mary alkyloxonium ion)... 

The —OH proton of a primary alcohol RCH2OH is vicinal to two protons and its sig nal would be expected to be split into a triplet Under certain conditions signal splitting of alcohol protons is observed but usually it is not Figure 13 21 presents the NMR spec trum of benzyl alcohol showing the methylene and hydroxyl protons as singlets at 8 4 7 and 2 5 respectively (The aromatic protons also appear as a singlet but that is because they all accidentally have the same chemical shift and so cannot split each other)... 

Synthesis Gas Chemicals. Hydrocarbons are used to generate synthesis gas, a mixture of carbon monoxide and hydrogen, for conversion to other chemicals. The primary chemical made from synthesis gas is methanol, though acetic acid and acetic anhydride are also made by this route. Carbon monoxide (qv) is produced by partial oxidation of hydrocarbons or by the catalytic steam reforming of natural gas. About 96% of synthesis gas is made by steam reforming, followed by the water gas shift reaction to give the desired H2 /CO ratio. 

Butter, fresh and salted, was once a primary trade commodity, but is no longer in as high a demand. There has been a shift in emphasis from fat content to the protein, mineral, and vitamin content of milk and milk products, particularly in developed countries. 

Steam-Reforming Natural Gas. Natural gas is the single most common raw material for the manufacture of ammonia. A typical flow sheet for a high capacity single-train ammonia plant is iadicated ia Figure 12. The important process steps are feedstock purification, primary and secondary reforming, shift conversion, carbon dioxide removal, synthesis gas purification, ammonia synthesis, and recovery. 

---