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Chemistry Of Petrochemical Processes 4

Chemistry Of Petrochemical Processes 4

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Refinery Pedia: Oil Refinery Processes, Gas Processing, Petrochemicals, courses, articles, books, videos ,and more...
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06/16/2012

 
CHAPTER FOUR
NonhydrocarbonIntermediates
INTRODUCTION
From natural gas, crude oils, and other fossil materials such as coal,few intermediates are produced that are not hydrocarbon compounds.The important intermediates discussed here are hydrogen, sulfur, carbonblack, and synthesis gas.Synthesis gas consists of a nonhydrocarbon mixture (H
2
,CO) obtain-able from more than one source. It is included in this chapter and is fur-ther noted in Chapter 5 in relation to methane as a major feedstock forthis mixture. This chapter discusses the use of synthesis gas obtainedfrom coal gasification and from different petroleum sources for produc-ing gaseous as well as liquid hydrocarbons (Fischer Tropsch synthesis).Naphthenic acids and cresylic acid, which are extracted from certaincrude oil fractions, are briefly reviewed at the end of the chapter.
HYDROGEN
Hydrogen is the lightest known element. Although only found in thefree state in trace amounts, it is the most abundant element in the uni-verse and is present in a combined form with other elements. Water, nat-ural gas, crude oils, hydrocarbons, and other organic fossil materials aremajor sources of hydrogen.Hydrogen has been of great use to theoretical investigation. The struc-ture of the atom developed by Bohr (Nobel Prize Winner 1922) wasbased on a model of the hydrogen atom. Chemically, hydrogen is a veryreactive element. Obtaining hydrogen from its compounds is an energy-extensive process. To decompose water into hydrogen and oxygen, anenergy input equal to an enthalpy change of +286 KJ/mol is required
1
:
111
 
H
2
O
r
H
2
+
1
 / 
2
O
2
H = +286 KJ/molElectrolysis, and thermochemical and photochemical decomposition of water followed by purification through diffusion methods are expensiveprocesses to produce hydrogen.The most economical way to produce hydrogen is by steam reformingpetroleum fractions and natural gas (Figure 4-1).
2
In this process, twomajor sources of hydrogen (water and hydrocarbons) are reacted to pro-duce a mixture of carbon monoxide and hydrogen (synthesis gas).Hydrogen can then be separated from the mixture after shift convertingcarbon monoxide to carbon dioxide. Carbon oxides are removed by pass-ing the mixture through a pressure swing adsorption system. The shiftconversion reaction is discussed in relation to ammonia synthesis inChapter 5. The production of synthesis gas by steam reforming liquidhydrocarbons is noted later in this chapter.Recently, a new process has been developed to manufacture hydrogenby steam reforming methanol. In this process, an active catalyst is usedto decompose methanol and shift convert carbon monoxide to carbondioxide. The produced gas is cooled, and carbon dioxide is removed:CH
3
OH(g) + H
2
O(g)
r
CO
2
(g) + 3 H
2
(g)
112
Chemistry of Petrochemical Processes
Figure 4.1.
Aprocess for producing hydrogen by steam reforming of hydrocar-bons:
2
(1) reforming furnace (2,3) purification section, (4) shift converter, (5) pres-sure swing adsorption.
 
This process is used to produce relatively small quantities (0.18–1.8MMscfd) of highly pure hydrogen when methanol is available at a rea-sonable price.In the petroleum refining industry, hydrogen is essentially obtained fromcatalytic naphtha reforming, where it is a coproduct with reformed gasoline.The use of hydrogen in the chemical and petroleum refining industriesis of prime importance. Hydrogen is essentially a hydrogenating agent.For example, it is used with vegetable oils and fats to reduce unsaturatedesters (triglycerides). It is also a reducing agent for sulfide ores such aszinc and iron sulfides (to get the metals from their ores).Hydrogen use in the petroleum refining includes many processingschemes such as hydrocracking, hydrofinishing of lube oils, hydrodealkyla-tion and hydrodesulfurization of petroleum fractions and residues. Hydro-cracking of petroleum resids is becoming more important to produce lighterpetroleum distillates of low sulfur and nitrogen content to meet stringentgovernment-mandated product specifications to control pollution.In the petrochemical field, hydrogen is used to hydrogenate benzeneto cyclohexane and benzoic acid to cyclohexane carboxylic acid. Thesecompounds are precursors for nylon production (Chapter 10). It is alsoused to selectively hydrogenate acetylene from C
4
olefin mixture.As a constituent of synthesis gas, hydrogen is a precursor for ammo-nia, methanol, Oxo alcohols, and hydrocarbons from Fischer Tropschprocesses. The direct use of hydrogen as a clean fuel for automobiles andbuses is currently being evaluated compared to fuel cell vehicles that usehydrocarbon fuels which are converted through on-board reformers to ahydrogen-rich gas. Direct use of H
2
provides greater efficiency and envi-ronmental benefits.
3
Due to the increasing demand for hydrogen, many separation tech-niques have been developed to recover it from purge streams vented fromcertain processing operations such as hydrocracking and hydrotreating.In addition to hydrogen, these streams contain methane and other lighthydrocarbon gases. Physical separation techniques such as adsorption,diffusion, and cryogenic phase separation are used to achieve this goal.Adsorption is accomplished using a special solid that preferentiallyadsorbs hydrocarbon gases, not hydrogen. The adsorbed hydrocarbonsare released by reducing the pressure. Cryogenic phase separation on theother hand, depends on the difference between the volatilities of the com-ponents at the low temperatures and high pressures used. The vaporphase is rich in hydrogen, and the liquid phase contains the hydrocar-bons. Hydrogen is separated from the vapor phase at high purity.
Nonhydrocarbon Intermediates
113

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