Petrochemical Products from Methane

Important chemicals based on methane, synthesis gas, ammonia, and methanol

Methane is a one-carbon paraffinic hydrocarbon that is not very reactive under normal conditions. Only a few chemicals can be produced directly from methane under relatively severe conditions.

CHEMICALS BASED ON DIRECT REACTIONS OF METHANE

1. Carbon disulfide, CS2 2. Hydrogen cyanide, HCN 3. Chloromethanes,

CH3Cl/CH2Cl2/CHCl3/CCl4
4. Synthesis gas mixture (Steam Reforming

of Natural Gas)
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1. Carbon disulfide, CS2

T = High ~675 degC Reaction = Exothermic Catalysts = Activated Alumina / Clay P = 2 atm Co-product = H2S Yield = 85-90% Alternative = reaction of liquid sulfur with charcoal
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Uses of Carbon Disulfide

1. Used to produce rayon and cellophane

(regenerated cellulose)
2. To produce carbon tetrachloride using

iron powder as a catalyst at 30C

Net reaction :
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3. To produce xanthates ROC(S)SNa as

an ore flotation agent and

4. To produce ammonium thiocyanate as

a corrosion inhibitor in ammonia handling systems

2. Hydrogen cyanide, HCN

Properties: A colorless liquid (b.p. 25.6C) that is miscible with water, producing a weakly acidic solution. It is a highly toxic compound, but a very useful chemical intermediate with high reactivity.

(a) Andrussaw process

Using ammonia and methane in presence of air. Reaction : Exothermic Catalyst : Platinum-rhodium alloy T : 1100 deg C Equal amounts of ammonia and methane with 75 vol % air are introduced to the preheated reactor.

(b) Degussa process

React ammonia with methane in absence of air Catalyst : platinum, aluminum-ruthenium alloy T : 1200 deg C Yield : 90% Reaction : Endothermic (251 KJ/mol)
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(c) Other Process

Reaction of ammonia and methanol in presence of oxygen

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Uses of HCN
To produce: Acrylonitrile Methyl methacrylates (from acetone) Adiponitrile Sodium cyanide Oxamide (a long-lived fertilizer that releases nitrogen steadily over the vegetation period)
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Oxamide
Produced by the reaction of hydrogen cyanide with water and oxygen Catalyst : copper nitrate P : Atmospheric T : 70 deg C

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3. Chloromethanes
Monochloromethane (methyl chloride, CH3Cl) Dichloromethane (methylene chloride, CH2Cl2) Trichloromethane (chloroform, CHCl3) Tetrachloromethane (carbon tetrachloride, CCl4)

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Production of Chloromethane
Most difficult alkane to chlorinate. The reaction is initiated by chlorine free radicals obtained via the application of heat (thermal) or light (hv).
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Thermal chlorination
T : ~350370C P : Atmospheric pressure

Product distribution among the chloromethanes depends primarily on the mole ratio of the reactants.

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Desired Yield
Monochloromethane could be increased to 80% by increasing the CH4/Cl2 mole ratio to 10:1 at 450C. Dichloromethane CH4/Cl2 ratio is lowered and the monochloromethane recycled. Decreasing the CH4/Cl2 ratio generally increases polysubstitution and the chloroform and carbon tetrachloride yield.
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Uses of Chloromethanes
Methyl chloride To produce silicon polymers (Major) Synthesis of tetramethyl lead as a gasoline octane booster, As methylating agent in methyl cellulose production As solvent As refrigerant
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Methylene chloride As paint remover As a degreasing solvent As blowing agent for polyurethane foams As solvent for cellulose acetate

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Chloroform To produce chlorodifluoromethane (Fluorocarbon22) by the reaction with hydrogen fluoride:

As a refrigerant As an aerosol propellent Used to synthesize tetrafluoroethylene, which is polymerized to a heat resistant polymer (Teflon)
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Carbon tetrachloride

Ozone depletion values for HCFC-123 and HCFC-22 relative to Freon-11 equals 0.02 and 0.055, respectively.

To produce chlorofluorocarbons (CFC) Catalyst : Antimony pentachloride (SbCl5)

Trichlorofluoromethane (Freon-11)

used as aerosols and refrigerants

Dichlorodifluoromethane (Freon-12)
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4. Synthesis gas mixture

Natural gas is the preferred feedstock when it is available from: 1. Gas fields (nonassociated gas) or 2. Oil wells (associated gas)

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treat natural gas to remove hydrogen sulfide Conditions:

Primary reformer

purified gas is then mixed with steam and introduced to the first reactor

steam to natural gas ratio varies from 45 (depending on natural gas composition and the pressure used) favored at high Catalyst : promoted nickel type T : 700800C P : 3050 atmospheres

temperatures, low pressures, and a high steam to carbon ratio

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Product gas from primary reformer

Mixture of H2, CO, CO2, unreacted CH4, and steam.

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Secondary reforming
Function: Remove carbon monoxide, which poisons the catalyst used for ammonia synthesis. Carry out via:
Shift conversion Carbon dioxide removal Methanation of the remaining CO and CO2 25

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Shift Conversion
CO is reacted with steam to give CO2 and H2. Reaction : exothermic and independent of pressure

Catalyst : iron catalyst promoted with CrO Temperature range : 425500C to enhance the oxidation
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Exit gases are treated to remove CO2.

1. By absorbing carbon dioxide in a

physical or 2. Chemical absorption solvent or 3. 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.
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Methanation

Reactions : exothermic Methane yield is favored at lower T and higher P. The space velocity becomes high with increased P, and contact time becomes shorter, decreasing the yield.

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Optimum Conditions
Catalyst : Rany nickel T : 200300C P : ~ 10 atm Product : a gas mixture of hydrogen and nitrogen having an approximate ratio of 3:1 for ammonia production
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ICI process for producing synthesis gas and ammonia

(1) desulfurization (2) feed gas saturator, (3) primary reformer, (4) secondary reformer, (5) shift converter, (6) methanator, (7) ammonia reactor.
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CHEMICALS BASED ON SYNTHESIS GAS

2 major chemicals based on synthesis gas are: 1. Ammonia (urea, nitric acid, hydrazine, acrylonitrile, methylamines)
2. Methanol

(formaldehyde, acetic acid, and methylamine)

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AMMONIA (NH3)
Properties:
colorless gas has an irritating odor very soluble in water forming a weakly basic solution easily liquefied under pressure
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Ammonia Production (Haber Process)

Increasing the temperature increases the reaction rate, but decreases the equilibrium. According to LeChateliers principle, the equilibrium is favored at high pressures and at lower temperatures.
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Optimum Conditions
Catalyst Iron oxide promoted with other oxides such as potassium and aluminum oxides

to produce ammonia in good yield at relatively low T

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Commercial process (NH3)

H and N (3:1) is compressed to the desired pressure (1501,000 atm) Reaction occurs over the catalyst bed at about 450C. Exit gas (ammonia) is passed through a cooling chamber where ammonia is condensed to a liquid, while unreacted hydrogen and nitrogen are recycled.
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UREA
White solid that is soluble in water and alcohol. Forms : crystals, prills, flakes, or granules An active compound that reacts with many reagents. By reacting with formaldehyde, it produces an important commercial polymer (urea formaldehyde resins) that is used as glue for particle board and plywood.
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Production

2 steps:
Ammonium carbamate is formed A decomposition step of the carbamate to

urea and water

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Snamprogetti process for producing urea

(1) reactor, (2,3,4) carbonate decomposers, (5,6) crystallizing and prilling

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Uses of Urea
80% : fertilizer field 10% : the production of adhesives and plastics (urea formaldehyde and melamine formaldehyde resins) 5% : Animal feed

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Nitric Acid (HNO3)

Colorless to a yellow liquid Very corrosive. A strong oxidizing acid that can attack almost any metal. Used to produce ammonium nitrate fertilizer
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Commercial Production
Nitric acid is produced by oxidizing ammonia with air over a platinumrhodium wire gauze. Reaction : Exothermic Optimum Conditions: T : 900C P : Atmospheric pressure

Catalyst

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Uses of Nitric Acid

Primary use Production of ammonium nitrate for fertilizers Secondary use Explosives Nitrating agent for aromatic and paraffinic compounds Steel refining Uranium extraction
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Hydrazine (H2N-NH2)
Colorless Fuming liquid miscible with water Weak base but a strong reducing agent Used as a rocket fuel because its combustion is highly exothermic and produces 620 KJ/mol

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Production of Hydrazine
Oxidation of ammonia using the Rashig process
Chloramine NH2Cl
oxidizing agent

NH3

Sodium hypochlorite

Hydrazine is then evaporated from the sodium chloride solution

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Puck process Oxidizing agent : hydrogen peroxide

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Uses of Hydrazine
Rocket fuel As a blowing agent Pharmaceutical Fertilizer industries Polymerization initiator (weak N-N bond) As a reducing agent (an oxygen scavenger for steam boilers)
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METHYL ALCOHOL (CH3OH)

1st member of the aliphatic alcohol family. Highly polar (hydrogen bonding) Evidenced by: relatively high boiling temperature (65C) high heat of vaporization low volatility
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Due to the high oxygen content of methanol (50 wt%), it is being considered as a gasoline blending compound to reduce carbon monoxide and hydrocarbon emissions in automobile exhaust gases.

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Initial Production by the destructive distillation of wood (wood alcohol) for charcoal production. Latest Technology mainly produced from synthesis gas.

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Methanol as an alternative fuel for gasoline cars

Problems:
1. Cold engine startability due to its high

vaporization heat (heat of vaporization is 3.7 times that for gasoline) 2. Lower heating value, which is ~ half that of gasoline, and 3. Corrosive properties.
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High reactivity of Methanol has allowed the following processes:

1. Oxidized to formaldehyde 2. Carbonylated to acetic acid 3. Dehydrated and polymerized to

hydrocarbons in the gasoline range (MTG process) 4. CH3OH + isobutene MTBE Tertiary 5. CH3OH + isoamylenes TAME
Both MTBE & TAME are important gasoline additives for raising the octane number and reducing carbon monoxide and hydrocarbon exhaust emissions. Amyl Methyl Ether
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Production of Methanol

A block flow diagram showing the combined reforming for methanol synthesis

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Produced by the catalytic reaction of CO and H2 (synthesis gas) An energy-efficient alternative to adjusting the CO:H2 ratio is to combine the steam reforming process with autothermal reforming (combined reforming) so that the amount of natural gas fed is that required to produce a synthesis gas with a stoichiometric ratio of approximately 1:2.05
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If an autothermal reforming step is added, pure oxygen should be used. (This is a major difference between secondary reforming in case of ammonia production, where air is used to supply the needed nitrogen)

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Why Combined Reforming?

The ratio of CO:H2 in synthesis gas from natural gas is approximately 1:3. The stoichiometric ratio required for methanol synthesis is 1:2. Carbon dioxide is added to reduce the surplus hydrogen. *Old Method
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Combined Reforming
Advantage Decrease in NOx emission. Disadvantage A capital cost increase (for air separation unit) of roughly 15% is anticipated when using combined reforming in comparison to plants using a single train steam reformer.
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Formaldehyde

Main industrial route : catalyzed air oxidation of methanol Old Process Dopant Catalyst : silver-gauze T : 500C New Process Catalyst : Iron-molybdenum oxide (Cr / CoO) T : 400425C at 1 atm
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Haldor Topsoe and Nippon Kasei process for producing formaldehyde

(1) blower, (2) heat exchanger, (3) reactor, (4) steam boiler, (5) absorber, (6,7) coolers, (8) incinerator, (9) heat recovery, (10) methanol evaporator, (11) boiler feed water.

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Uses of Formaldehyde
Simplest and most reactive aldehyde Condensation polymerization of : *GLUES

F + phenol phenol-formaldehyde F + urea urea formaldehyde F + melamine melamine formaldehyde

resins *used in producing particle board and plywood

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Uses of Formaldehyde
Condensation of formaldehyde with acetaldehyde in presence of a strong alkali produces pentaerythritol, a polyhydric alcohol for alkyd resin

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Uses of Formaldehyde
Formaldehyde reacts with ammonia and produces hexamethylenetetramine (hexamine):

Hexamine is a cross-linking agent for phenolic resins.

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