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4 - Synthesis Gas

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13 views13 pages

4 - Synthesis Gas

Uploaded by

Ali Hussein
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Lecture (4)

Third Year – Petroleum Refinery. Branch


Chemicals from Petroleum Lectures
By
Dr. Adnan A. Abdul Razak
Introduction
Synthesis Gas
• Methane and synthesis gas are important petrochemical feedstock for
manufacture of a large number of chemicals, which are used directly or as
intermediates.
• Many of these products are funding use in plastic, synthetic fiber, rubber,
pharmaceutical and other industries.
Q/ Methane and synthesis gas are important petrochemical feedstock for many products such as?

• ‘Synthesis gas’ is commonly used to describe two basic gas mixtures -


synthesis gas containing CO, hydrogen and synthesis gas containing hydrogen
and nitrogen for the production of ammonia.
Q/ What are the synthesis gas mixtures?
Q/ Synthesis gas mixture of hydrogen and nitrogen is used for production ____?

Synthesis Gas
• Petrochemical derivatives based on synthesis gas and carbon monoxide have
experienced steady growth due to large scale utilization of methanol and
development of carbonylation process for acetic acid and oxo synthesis process
for detergents, plasticizers, and alcohols.
Raw Materials for Synthesis Gas Production
• Various raw materials for synthesis gas production are natural gas, refinery
gases, naphtha, fuel oil/residual heavy hydrocarbons and coal, and Petrocoke.
Q/ The synthesis gas have produced from____?
Petrocoke is a final carbon-rich solid material that derives from oil refining, and is
one type of the group of fuels referred to as cokes.
Q/ What is Petrocoke?

Hydrogen production from HCs feed


1- Steam reforming of light ends such as methane (natural gas), ethane, or propane.
2- Partial oxidation of heavy hydrocarbons such as fuel oil.
Q/ What are the ways for synthesis gas production from hydrocarbons feed?
Q/ Explain one way for synthesis gas production from hydrocarbons feed?
1. Steam reforming
Steam reforming for hydrogen production is accomplished in four steps:
1. Reforming. 2. Shift conversion. 3. Gas purification. 4. Methanation.

Q/ What are the steps for the steam reforming for hydrogen production?

1. Reforming. This involves the catalytic reaction of methane with steam at


temperatures in the range of 1400 to 1500 °F (760–816 °C), according to the
following equation:
CH4 + H2O → CO + 3H2 )1( ‫مطلوبة‬
This reaction is endothermic and is carried out by passing the gas through
catalyst-filled tubes in a furnace. The catalyst usually is in the form of hollow
cylindrical rings ranging up to 3/4 inch in diameter. It consists of 25 to 40%
nickel oxide deposited on a low-silica refractory base.
Q/ Why is the catalyst usually in the form of hollow cylindrical rings ranging up to 3/4 inch in diameter?
Ans/ 1- For the gas to flow in the reactor without stream plugging.
2- To increase the catalyst surface area to increase the contact between methane and steam.
2. Shift conversion. More steam is added to convert the CO from step 1 to an
equivalent amount of hydrogen by the following reaction:
CO + H2O → CO2 + H2 )2( ‫مطلوبة‬
This is an exothermic reaction and is conducted in a fixed-bed catalytic reactor at
about 650 °F (343 °C). Multiple catalyst beds in one reactor with external
cooling between beds are commonly employed to prevent the temperature from
getting too high. The catalyst used is a mixture of chromium and iron oxide.
Q/ Why the reactor in shift conversion needs cooling?
Ans/ Because the reaction of CO conversion to an equivalent amount of hydrogen is an exothermic
reaction.

3. Gas purification. The third step is removal of carbon dioxide by absorption in a


circulating amine or hot potassium carbonate solution. Several other treating solutions are
in use. The treating solution contacts the hydrogen and carbon dioxide gas in an absorber
containing about 24 trays, or the equivalent amount of packing. Carbon dioxide is
absorbed in the solution, which is then sent to a still for regeneration.
4. Methanation. In this step, the remaining small quantities of carbon
monoxide and carbon dioxide are converted to methane by the following
reactions:
CO + 3H2 → CH4 + H2O
CO2 + 4H2 → CH4 + 2H2O (3)
This step is also conducted in a fixed-bed catalytic reactor at temperatures of
about 700 to 800 °F (427 °C). Both reactions are exothermic and, if the feed
concentration of CO and CO2 is more than 3%, it is necessary to recycle some
of the cooled exit gas to dissipate the heat of reaction. The catalyst contains 10
to 20% nickel on a refractory base.

Q/ How could the methanation reactor be cool?


Ans/ by recycling some of the cooled exit gas to dissipate the heat of reaction.

Q/ Explain the four steps?


CH4 + H2O → CO + 3H2 (Steam Reforming)
CO + H2O → CO2 + H2 (Shift Convertor)
CO + 3H2 → CH4 + H2O (Methanation)
CO2 + 4H2 → CH4 + 2H2O
2. Partial oxidation of fuel oils
a- Partial oxidation of fuel oils is accomplished by burning the fuel at high pressures (800 to
1300 psig) with an amount of pure oxygen which is limited to that required to convert the
fuel oil to carbon monoxide and hydrogen.
Q/ Why is the pure oxygen limited in partial oxidation of fuel oils?
Ans/ To prevent the complete conversion of hydrocarbons to carbon dioxide and water.

b- Enough water (steam) is added to shift the carbon monoxide to hydrogen in a catalytic
shift conversion step.
c- The resulting carbon dioxide is removed by absorption in hot potassium carbonate or
other solvents.
d- Ideally the partial oxidation reactions are as follows:
2CnHm + nO2 → 2nCO + mH2
2nCO + 2nH2O → 2nCO2 + 2nH2

Q/ Explain Partial oxidation of fuel oils for synthesis gas production?


Partial Oxidation Characteristics
1- Flexibility of use of HCs fuel, petroleum fraction, crude oil with high sulfur content
and residue.
2- It is used when NG or light fractions is not available or when its prices are high.
3- Dose not need catalyst.
4- Need of oxygen unit to produce pure oxygen.

Q/ What are the characteristics of the partial oxidation to produce synthesis gas?

Basic steps:
1- Gasification:
a- Process occur in reactor lined with fire bricks without catalyst.
b- Reaction occurs between primary heated feed with oxygen and steam
which is supplied through burners.
c- T=1300-1500 °C P=Higher than 10 atm. (40-90 atm.)
2- Cooling:
Two types according to companies:
a- Quench system: Texaco process.
b- W.H.B.: Shell process.
3- Removal of soot.
4- Conversion of CO to CO2
5- Removal of CO2, H2S.
6- Removal of inert gases like Ar, Co.
7- Compression of resultant gases (H2) or mixture (CO, H2)

Q/ What are the basic steps of partial oxidation to produce synthesis gas?
?Q/ Compare between steam reforming and partial oxidation to produce synthesis gas
Emerging Technologies in Utilization of Synthesis Gas and Methane for
Production of Petrochemicals:
• Methanol to Olefin technology (MTO). Oxidative coupling of methane to yield
ethane and ethylene.
• Fischer-Tropsch synthesis is being studied in great detail world over and it is
promising to be a future technology for manufacture of olefins from synthesis gas.
• CO that can be separated from synthesis gas either by cryogenic or by
pressure swing adsorption is a promising feedstock for production of variety of
products.

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