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Steam reforming (Hydrogen) Synthetic gas (CO + H2) Cracking (hydrocarbons)

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Lightest element.

Most abundant element in the universe; free state in trace amounts; present in combined form with other elements.
Major source - water, natural gas, crude oils, and other organic fossil materials. Bohrs structure of atom based on model of hydrogen atom Very reactive atom obtaining hydrogen from its compound is an energy extensive process. Eg: water splitting 286kJ/mol

 Production:
Requires high energy so expensive Electrolysis, Steam reforming, Partial oxidation By-product of catalytic reforming units

Annual world hydrogen production is around 5 x1011 Nm3 corresponding to around 2% of primary energy consumption.
Source: Ewan and Allen (2005), Int. J. of Hydrogen Energy, Vol., 30, pp.809-819

Hydrogen Production Processes (new)

Steam Reforming Process substrate (CnHmOp) + steam carbon oxides + hydrogen H>0 Partial Oxidation Process substrate (CnHmOp) + air carbon oxides + hydrogen +nitrogen H<0 Aqueous Reforming Process High Pressure and Low temperature but still an endothermic reaction H>0 Autothermal Reforming Process substrate (CnHmOp) + air + steam carbon oxides + hydrogen +nitrogen H=0

Source: Adhikari et al., (2009) Energy Conversion and Management 50 (2009) 2600 2604

 Steam reforming of petroleum fractions and natural gas

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For light HCs like methane, ethane, or propane, methanol (when methanol price is reasonable) Overall reaction:

Reactionsinvolved in steam reforming of HCs

 Steam reforming of petroleum fractions and natural gas

! 4 steps

1. Reforming: CH4 + H20 CO + 3 H2 (1400 1500oF; Catalyst: Nickel oxide on low-silica refractory base) 2. Shift conversion (WGS): CO + H2O CO2 + H2 (Exothermic; 650oF; Catalyst: Oxide of Cr or Fe) 3. Gas purification: CO2removed by passing mixture through a P swing adsorption system or absorbing in a circulating amine or hot potassium carbonate solution 4. Methanation: CO + 3H2 CH4+ H2O CO2 + 4H2 CH4+ 2H2O (Exothermic; 700 - 8000oF; Catalyst: : Nickel on refractory base)

 Catalytic naphtha reforming

! produces H2 as co-product with reformed gasoline.

 Separation techniques recover H2 from hydrocracking and hydrotreating products H2 + light HC gases
Adsorption, cryogenic phase separation, diffusion

Adsorption:
special solid that adsorbs HC gases HCs released by reducing P

Cryogenic phase separation

depends on diff between volatilities of components at low T & high P (-200 to -250oF, 200 to 500 psig) vapor phase rich in H2 (pure) liquid phase rich in HCs

Diffusion
depends on permeation rate for gas mix passing through special membrane permeation rate type of gas feed, membrane material, operating conditions small molecule size (He, H) permeate membranes more readily/easily

 membrane separator:
feed gas is preheated and filtered gas mix is distributed in annulus between fiber bundle and vessel wall H2 diffuses through hollow fiber wall and exits at lower P HCs less permeable flow around fiber walls to a perforated centre tube and exits at ~feed P provides >95% pure H2

 Electrolysis

2H 2O 2H 2 + O 2 2HF H 2 + F2 2HCl / H 2O H 2 + Cl 2 2NaCl / H 2O H 2 + Cl 2 + NaOH

Uses: Hydrogenating agent

used with vegetable oils to reduce unsaturated esters for sulphide ores to remove metal compounds (Zn, Fe)

Processing schemes
hydrocracking, hydrofinishing, hydrodealkylation, hydrodesulphurization, etc.

Precursors
ammonia, methanol, oxo alcohols, HCs from Fisher Tropsch processes.

Hydrogenate benzene (and derivatives)

Benzene cyclohexane benzoic acid cyclohexane carboxylic acid compounds are precursors to nylon production

Clean fuel
for land vehicles currently being evaluated

7068/5797*4:7*
Refers to a mixture of CO + H2 H2:CO varies according to feed type, production methods, and end use of the gases. Germans obtained synthesis gas by gasifying coal during WW II:
Product mix - produce liquid HC mix in gasoline range using Fischer Tropsch technology Route was abandoned due to high cost to produce HCs Method is still being used in South Africa (Sasol) inexpensive coal Alternate feedstocks for syngas is being examined.

 Production
steam reforming partial oxidation gasifying coal
of HCs ranging from CH4 to heavy petroleum residues

Gasifying coal
gasifying coal to medium Btu gas (consists of CO, CO2, H2) used principally as fuel gas

Steam reforming natural gas

over nickel catalyst at approximately 800 C

route is used when natural gas is abundant and inexpensive Saudi Arabia and USA

Steam reforming naphtha

used in Europe naphtha HCs ranging from C5-C10; eq represented by n-heptane:

as MW of HCs increases (lower H:C feed ratio), the H2:CO product increases. H2:CO for methane is 3; 2.5 for ethane; 2.1 for heptane; <2 for heavier HCs

Non-catalytic partial oxidation

H2:CO lower than steam reforming in practice, the ratio is lower since part CH4 is oxidized to CO2 + H2O T = 1400-1450 C; P = 55-60 atm equal ratios of H2/CO Refer Table 4-2

 Partial oxidation of petroleum fractions

H2S

 USES Important intermediate used for producing CH4OH.

Also used to synthesize HCs gases, naphtha, gas oil, etc using Fischer Tropsch technology.
Alternative route for olefins and chemicals.

Forms oxo aldehydes and alcohols hydroformylation reaction (oxo synthesis) when reacted with olefins.
H2 used in production of ammonia produce urea, ammonium nitrate, hydrazine.

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Important industrial synthetic raw material Usage: 90% is used in chemical Industry; 10% for energy Manufacture: from Syngas

CO + 2H2 CH3OH

H = 92kJ / mol

 USES Uses of methanol in worldwide (%)

Future uses:
1. Motor fuel/ gasoline component 2. Energy source 3. Feedstock for many chemical synthesis

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Reactants CO and H2 Reaction hydrogenative oligomerization of CO in the presence of heterogeneous catalyst. Main reactions:

Source: Olav A. Opdal, 2006. Production of synthetic biodiesel via Fischer-Tropsch synthesis

Source: Burtron H. Davis, 2009. Catalysis Today 141 (2009) 2533

Side reaction: Co-product H2O Reacts with CO (the shift reaction) H2 + CO2 H2 produced - reduces hydrogen demand for FTS feed. Shift reaction proceeds at same rate as FTS reaction. Another side reaction occurs:

Reaction is responsible for deposition of C in reactor tubes in fixed-bed reactor; and reduces heat transfer efficiency.

 Reactors:

Source: Spath and Dayton, 2003. NREL/TP-510-34929

 Fixed bed:
run at lower T to avoid C deposition on reactor tubes. products low olefin content, heavier products than fluid bed

Fluid bed:
better heat distribution operates at high T products- have more olefins, high % of light HC gases, lower MW products

Catalyst: Uses transition metals iron, nickel, cobalt

Iron - preferred due to low cost and higher activity; produces HCs + CO2; high tolerance for sulfur, produce more olefin and alcohols
Nickel produces large amounts of methane Cobalt has lower reaction rate and lower selectivity; produces HCs + H2O; high conversion rate, a longer life

Iron catalysts promotes shift reaction better than Co catalysts

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Physical Separation processes
Atmospheric distillation Vacuum distillation Absorption Adsorption Solvent extraction

Chemical Conversion processes

Thermal processes
Coking process, Viscosity breaking, Thermal cracking

Catalytic processes
Reforming, cracking, hydrocracking, hydrodealkylation, isomerization, aromatization

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Increase the amount of middle distillates Produces lubricating oil base stock and asphalt Feed: residue from atmospheric distillation

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Three basic routes
Cracking (Thermal decomposition) For selected petroleum fractions in order to produce unsaturated hydrocarbons like ethylene Chemical transformation For petroleum fractions of suitable C-number range are isolated and subjected for chemical conversion without an intermediate cracking step Catalytic reforming Catalytic treatment in presence of hydrogen; a variety of reactions take place; to improve the octane number of gasoline in refining;

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By various cracking operations The yields of products vary with the intensity of cracking Steam cracking
Most widely used cracking technique for olefin production

Kellogg Adiabatic process

More intense cracking Higher feedstock like naphtha, gas oil Superheated steam at 900 oC High yield for ethylene and low carbon formation

Specialized cracking of paraffin waxes

Feedstock has wide C-number distribution

 Steam cracking of hydrocarbons

Main route for producing light olefins, especially ethylene Feedstocks: various petroleum fractions and residue, light paraffinic hydrocarbons from natural gas Superheated steam is used to reduce the partial pressure of reactants to reduce carbon deposition, reacts with carbon and remove it as carbon monoxide and hdrogen (steam reforming) act as a diluent which reduces the hydrocarbons chances of being in contact with the reactor wall

Highly endothermic dehydrogenation High temperature, low pressure Eg:

During cracking, many side reactions occur due to the formation of free radicals or beta scission of C-C bond These free radicals may terminate by abstraction of a hydrogen atom or it may continue cracking to yield further olefins When ethane is cracked to give ethene, propene and 1-butene are also produced Catalytic coking is a significant problem. Ni and other metal alloys in tubing catalyze dehydrogenation and coking Using better grade alloys for tubing reduced the severity of problems

 Process variables
Temperature
Endothermic process high temperature favors production of olefins and aromatics. Optimum temperatures are usually selected to maximize olefin production and minimize coke formation. Temperature also depends on feedstock (higher MW hydrocarbons crack at lower temperature and viceversa)

Residence time
Shorter residence time is required for high olefin yield (avoid secondary reactions to produce aromatics) 0.5 to 1.2 Sec are typical

Steam to hydrocarbon ratio

High Steam/Hydrocarbon weight ratio favors olefin formation (0.2 1 for ethane, 1-1.2 for liquid feeds)

Feedstocks
Vary from light hydrocarbon gases to petroleum residues. Operation parameters vary with the feedstock

As feedstocks progress from ethane to heavier fraction with lower H/C ratios, the yield of ethylene decreases, yields of by-products and aromatics increases Paraffinic hydrocarbons are easier to crack than cyclic paraffins, and aromatics tend to pass through unaffected Propane cracking is similar to ethane except for the furnace temperature (longer chain crack easier). However more byproducts are formed. Give higher yields for propylene and butadiene. However, as severity of cracking increases, the ethylene and gas yields increase

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Production of butadiene (CH2=CH-CH=CH2)
By-product from ethylene production, separated from C4 fraction using extractive distillation using furfural Also by the catalytic dehydrogenation of butanes or butane/butene mixture (lummus process) In some part of world (Russia), fermented alcohol can serve as a cheap source of butadiene
Vapor phase reaction Normal or reduced pressure Catalyst - ZnO/Al2O3 or Magnesia promoted with Cr or Co Intermediate: Acetaldehyde

Also by the reaction of acetylene and formaldehyde in the vapor phase over a copper acetylide catalyst

 Production of Isoprene (CH2=C(CH3)-CH=CH2)

Dehydrogenation of C5 olefin fractions from cracking process, several schemes are used for its manufacture via synthetic routes

1. Dehydrogenation of tertiary amylenes (2-methyl-1-butene or 2-methyl-2-butene)

Amylenes are extracted from C5 fraction with aqueous H2SO4 ; dehydrogeation over catalyst give isoprene Amylenes are also produced by reaction of ethylene and propene using acid catalyst

2. From acetylene and acetone

Reaction of acetylene and acetone in liquid ammonia in presence of alkali metal hydroxide methylbutynol hydrogenated to methylbutenol dehydrated at 250 300 oC over acidic catalyst

3. Isobutylene and formaldehyde

4. From Isobutylene and methylal(dimethoxy methane)

5. From Propylene

Dimerization of propylene to 2-methy-1-pentene (200 oC, 200 atm, tripropyl aluminium catalyst combined with Ni or Pt); isomerization of 2-methy-1-pentene to 2-methy-2-pentene (on acid catalyst); pyrolyzed to isoprene