Project Training At Indian Oil Corporation (R&D)

Capture of CO2 from a refinery gaseous stream and its further Utilization.

Under the guidance of Mr. Rajesh M. Badhe(PSM)

Submitted By: SHIVA ROHIT 100801058

Company Overview
Innovation through sustained process of R&D is the edge tool for the organization. INDMAX, a hallmark technology developed at R&D. Licensed the diesel hydro-treating technology in its two plants. Standing in the company of six worldwide technology holders for marine Oils. The R&D Centre continues to provide significant support to the Indian Oil Group refineries in product quality improvement and various other processes.

Project Overview
Expansion in refineries have led to emissions of gases like CO2, SO2, NOx, SOx etc. Various methods could be employed to capture the CO2 like absorption, membrane technology etc. The method employed at IOCL R&D is the absorption process by use of amines like MEA, MDEA, etc.
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What is Need of removing CO2

Accumulation of CO2 lead to serious climatic changes. It takes centuries to stabilize the effect of CO2. It can lead to changes in thermal structure of earth leading to rise in temperature of earth and increasing the water level.

Sources of CO2 in a refinery

1. Fuel for process heating, steam raising and power generation 2. Hydrogen production 3. Coke burn-off from the FCC

Ways to capture CO2

The two most commonly processes being used to capture CO2 are: Absorption process. Membrane technology.

Absorption process
Mainly done by the use of amines. Amines that are mainly used for this purpose are: 1. Methyl ethanolamine (MEA) 2. Methyl di-ethanolamine (MDEA)

Methyl Ethanolamine
Its structure is : It is an alkanolamine and toxic flammable corrosive colorless viscous liquid. It is a useful intermediate in the chemical synthesis of various products including polymers and pharmaceuticals. It is also used as a solvent.
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Methyl-diethanolamine (MDEA)
Its structure is It is an alkalonamine used in hydrogen sulphide enrichment units to selectively remove the hydrogen sulphide . It is also used in natural gas plants for removal of carbon dioxide.

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Capturing carbon dioxide with MEA

CO2

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MEA v/s MDEA

Major advantages in using MDEA over MEA are: High solution concentration (up to 50-55 wt.%). High acid gas loading. Low corrosion even at high solution loadings. Slow degradation rates. Lower heats of reaction. Low vapor pressure and solution losses.

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Membrane technology
Membrane systems have major advantages over more- traditional methods of CO2 removal: Lower capital cost Lower operating costs Operational simplicity and high reliability Adaptability Design efficiency Power generation
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Flow Scheme

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Membrane Pretreatment
Liquids cause swelling of the membranes and destruction of membrane integrity. Heavy hydrocarbons slowly coat the membrane surface, thus decreasing permeation rate. Particles can block the membrane flow area. Certain corrosion inhibitors and well additives are destructive to membranes.
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Traditional Pretreatment
Feed Adsorbent Guard Bed

Filter

Particle Filter

Heater

Membrane

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Additions to Traditional Pretreatment

Chiller:1. Reduce the dew point of gas. 2. Lower down the heavy hydrocarbon content. Turboexpander:Serve the same purpose as chiller but has a benefit of being a dry system. Glycol Unit:1. Added upstream to chiller to prevent hydrate formation. 2. Adsorbent guard bed is needed for removing heavy hydrocarbon.

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Need for Enhanced Pretreatment

1. Enhanced pre-treatment system that can better handle higher or fluctuating heavy hydrocarbon levels. 2. The pretreatment system did not have sufficient flexibility to handle such a wide departure from the design conditions. 3. The adsorbent bed was fully saturated within a short time, leading to performance degradation. 4. The preheaters were not large enough to achieve feed temperatures that were much higher than designed.

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Enhanced Pretreatment scheme

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Thermodynamic considerations of CO2 conversion

CO2 is highly stable molecule. CH4 +H2OCO+3H2O; (1) CH4 +CO22CO+2H2O; (2) It is more energy-demanding if one were to use only CO2 as a single reactant, but it becomes easier thermodynamically if CO2 is used as a co-reactant with another substance that has higher Gibbs free energy, such as CH4, carbon (graphite) and H2.
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Pilot Plant at IOCL

H2 CO2 CH4

Ss
Absorber

NaOH Solution
T=RT P= 5-7 atm

Reaction: - 2NaOH + CO2 Na2CO3 + H2O

H2+ CH4
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Plant Specifications
Pressure Temperature Concentration of H2 Concentration of CH4 Concentration of CO2 Concentration of NaOH Volume of NaOH in Absorber 5-7 atm Room Temperature 20% 75% 5% 3-10% 70 Lit

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Sample Calculation
1. Feed rate = 0.5 Nm3/hr Reaction: - 2NaOH + CO2 Na2CO3 + H2O 2 mole NaOH 1 mole CO2 80g NaOH 44g CO2 Or 1g CO2 (20/11)g NaOH Feed Concentration H2 =20% CO2= 5% CH4 =75% Feed Rate= 0.5 Nm3/hr = (1000*0.5)/22.4 mole/hr = 22.32 mole/hr Or Flow rate of CO2 = 0.05*22.32=1.11 mole/hr =1.11*44= 49.107g/hr Density of NaOH Solution= 2130 g/l Concentration of NaOH= 3% Volume of NaOH=70 lit Or Wt of NaOH= 70*0.03*2130=4473g Since 1g CO2 (20/11)g NaOH 49.107g/hr CO2 (20/11)* 49.107 NaOH =89.28 g/hr NaOH Or Saturation time=4473/89.28=50.097 hrs

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Observation Table
Flow Rate of Feed= 0.5 Nm3/hr
Concentration of NaOH
3% 5%

Flow Rate of Feed= 1 Nm3/hr

Concentration of NaOH
3% 5%

Saturation Time
50.097 hrs 83.501 hrs

Saturation Time
25.050 hrs 41.750 hrs

7%
10%

116.901 hrs
167.002 hrs

7%
10%

58.450 hrs
83.501 hrs

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NEWLY INSTALLED PLANT

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Plant Specifications
Pressure Temperature Concentration of H2 Concentration of CH4 Concentration of CO2 Concentration of MDEA+PZ+H2O Volume Absorber 5-7 bar Room Temperature 20% 75% 5% 3-10% 70 Lit

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Using CO2 as a mild oxidant

Some heterogeneous chemical reactions can benefit from using CO2 as a mild oxidant The use of CO2 has been found to be beneficial for selective dehydrogenation of ethylbenzene to form styrene Adding CO2 to the oxidation reactions of alkylaromatics with O2 enhanced the rate of reaction and improved the selectivity towards the aldehyde and oxygenates products.
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Use of CO2 for supercritical fluid extraction

CO2 can be used as either a solvent for separation or as a medium for chemical reaction, or as both a solvent and a reactant. Contaminant-free supercritical extraction of various substances ranging from beverage materials and organic and inorganic functional materials to herbs and pharmaceuticals. Reactive extraction of organic acids has been studied using supercritical CO2 for separation of citric acid and acetic acid from their aqueous solution. Recently SC-CO2 has become useful even for inorganic materials synthesis and processing.
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Conclusions
Caustic solution is not environmental friendly, so using a amine for absorption is a better choice. While using the caustic solution the absorbing bed gets saturated very early, so using amine instead of caustic solution as an absorbing solvent might not render the bed saturated that early as caustic solution. Membrane technology is not very common technique these days, but it might prove economical in the long run due to its large advantages like lower capital cost, lower operating cost, adaptability, operational simplicity etc.
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