Distillation (D-86) True Boiling Point

Asst. Prof. Dr. Pakamas Chetpattananondh In House Practical Training (IHPT)

Department of Chemical Engineering, Faculty of Engineering, PSU

Vaporization of pure component

212 F

70 F

Does "Boiling" Mean "Hot"?

Boiling occurs when the vapor pressure inside the bubble equals atmospheric pressure. What would happen if the atmospheric pressure would drop? The simple example of this is the case of a camper who is on the top of a 10,000 ft mountain. While water boils at 100 degrees C at sea level (where the atmospheric pressure is 760mm Hg) the atmospheric pressure at 10,000 ft altitude is about 530 mm Hg. Because the boiling point of water is about 90 degrees C at this altitude, not only will our camper find that his food will cook a little slower than normal, any attempt to boil water to kill germs and pathogens may be unsuccessful since the water isn't getting hot enough.

Vaporization of mixtures

Pure ethanol BP = 173 F

Batch distiallation

Continuous distillation

Volatility
A fuels ability to vaporize or change from liquid to vapor is referred to as its volatility. The volatility characteristics of a spark ignition (SI) engine fuel are of prime importance. Fuels that do not vaporize readily may cause hard starting of cold engines and poor vehicle driveability during warm-up and acceleration. Conversely, fuels that vaporize too readily at higher operating temperatures will cause too much vapor to form causing a decrease in fuel flow to the engine (known as vapor lock).
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Volatility
Volatility too low Volatility too high
Poor cold start High evaporative emissions, Canister overload & Purge Poor warm up performance Hot driveability problems, Vapor lock Poor cold weather driveability Fuel economy may deteriorate Unequal fuel distribution in carbureted vehicles Increased deposits: crankcase, spark plugs, combustion chamber
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Volatility
The main parameters to establish volatility limits are Vapor/Liquid Ratio (V/L), Vapor Pressure (RVP), and Distillation Curve. The vapor/liquid ratio uses a test to determine the temperature required to create a V/L ratio of 20. More volatile fuels require lower temperatures to achieve this ratio while less volatile fuels require higher temperatures to create the same ratio. The V/L ratio assists in defining a fuel's tendency to contribute to vapor lock. The V/L ratio and RVP are measurements of a fuel's "front end volatility", or more volatile components which vaporize first. The distillation test is used to determine fuel volatility over the entire boiling range of gasoline.
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Classification methods of petroleum fractions by boiling point

ASTM-D86: Distillation method for light petroleum products
ASTM D-1160: Distillation method for heavier fractions (>500F) carried out in vacuum

ASTM-D2892:
True Boiling Point (TBP)

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How is D-86 important ?

D 86 is used to determine

fuel volatility across the entire boiling range of fuel.

A = Front End (020% evaporated) B = Mid-range (20-90% evaporated) C = Tail End (90-100% evaporated)

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How is D-86 important ?

The 10% evaporated temperature must be low enough to provide easy cold starting but high enough to minimize vapor lock as well as hot driveability problems. The 50% evaporated temperature must be low enough to provide good warm up and cold weather driveabiity without being so low as to contribute to hot driveability and vapor locking problems. The 90% and end point evaporation temperatures must be low enough to minimize crankcase and combustion chamber deposits as well as spark plug fouling and dilution of engine oil.
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Flexible Volatility Index (FVI) This is a parameter calculated from the RVP and the measured value of E70, and is an indicator of the hot running performance (the tendency for vapour lock). FVI = RVP + (0.7 x E70)
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Using distillation curve

In New Zealand E 70C at 25-45% E 100C at 45-67%

DI = 1.5 x T10 + 3 x T50 + T90

DI for UL 91 is about 495 DI 550 cause driveability problem in cold

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True boiling point

ASTM D-2892 is used for samples with a wide boiling range such as crude petroleum up to a final cut temperature of 400C (752F) atmospheric equivalent temperature (AET). Theoretical plate = 14-18 (15) Distillation pot, volume = 15 L Volumetric of feed 5 10 L Reflux ratio = 5:1 Temperature of distillation 350C (AET) Weight loss 4%

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True boiling point

It is often useful to extend the boiling point data to higher temperatures than are possible in the fractionating distillation method and for this purpose a vacuum distillation in a simple still with no fractionating column (ASTM D-1160) can be carried out. This distillation, which is done under fractionating conditions equivalent to one theoretical plate, allows the boiling point data to be extended to about 600C (1112F) with many crude oils. This method gives useful comparative and reproducible results that are often accurate enough for refinery purposes, provided significant cracking does not occur. Usually seven fractions provide the basis for a reasonably thorough evaluation of the distillation properties of the feedstock:
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True boiling point

1. Gas, boiling range: <15.5C (60F) 2. Gasoline (light naphtha), boiling range: l5.5149C (60300F) 3. Kerosene (medium naphtha), boiling range: 149232C (300450F) 4. Gas oil, boiling range: 232343C (450650F) 5. Light vacuum gas oil, boiling range: 343371C (650700F) 6. Heavy vacuum gas oil, boiling range: 371566C (7001050F) 7. Residuum, boiling range: >566C (1050F)

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Typical Refinery Products

Product Boiling Range Deg. C
-40 - 0 30 - 200 170 - 270 180 - 340 340 - 540 340 - 650 540 + Solid

Boiling Range Deg. F

-40 - 31 80 - 400 340 - 515 350 - 650 650 - 1000 650 - 1200 1000 +

LPG Gasoline Kerosene, Jet Fuel, #1 Diesel #2 Diesel, Furnace Oil Lube Oils Residual Oil Asphalt Petroleum Coke

From: Schmidt, G.K. and Forster, E.J., Modern Refining for Todays Fuels and Lubricants, SAE Paper 861176, 1986.

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Crude Assay
EP

{
Cut points

Te

Tb Ta

vacuum gas oil

IBP
0% 20% 40% 60% 80% 100%

heavy gas oil

naphtha kerosene light gas oil

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Specification New Zealand Euro 3 (2000)

Parameter T85 E25019 E350 T95 T90 T95 Final boiling point

Limit 350C max. <65 % by volume 85% by volume min. 350C max. 340C (Cat.1) - 320C (Cat. 3&4) 355C (Cat.1) - 340C (Cat. 3&4) 365C (Cat.1) - 350C (Cat. 3&4) 370C max. from 1 January 2002 360C max. from 1 January 2006 330 - 360? C depending on cold weather class 338C max.

World-Wide Fuel Charter

Australia

T95

Japan USA

T90 T90

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For vacuum residues a typical true boiling point (TBP) cut point is 538C, but it may be lower or higher depending on the crude. The TBP cut point will define the concentration of Conradson carbon residue (CCR), sulfur, and metals in the feed and thereby affect yields and product quality.

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Thanks for your attention

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