Generation of TBP data using ASTM distillation

LABORATORY PROJECT GUIDED BY : DR. H.K. MOHANTA

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE, PILANI

Acknowledgement

TABLE OF CONTENTS

1. INTRODUCTION 5 2. TBP APPARATUS..6 3. ASTM METHODS FOR CRUDE CHARACTERISATION..7 4. PRINCIPLES INVOLVED8 5. APPARATUS10 6. PROCEDURE.12 7. OBSERVATION.14 8. CALCULATION..16 9. RESULTS18 10. CONCLUSION..20 11. REFERENCES22

Having in mind that crude oil cost accounts for more than 80% of refinery expenditure the proper operation of crude distillation unit has great impact on refinery profitability. In order to find the adequate technological regime that provides maximum yields of high value

products in a crude distillation unit the process engineer needs to have laboratory analyses data of crude oil that is processed in the unit. Distillation characteristics of a crude are assessed by performing a preliminary distillation called True Boiling Point analysis (TBP). This pulse test enlightens the refiners with all possible information regarding the percentage quantum of fractions, base of crude and the possible difficulties beset during treatment operations etc. Information supplied by this distillation forms the basis of design of distillation columns and thus represents the veridity of crude distillation.

The basic methods for determining the TBP data for a sample are: (1) To actually perform a TBP distillation, which is time consuming procedure ( 2 ) to perform single theoretical plate distillation (designated by the American Society for Testing and Materials as Method D-86 for atmospheric distillations , and Method D-11602 for vacuum

distillations), and converting the data mathematically with help of

correlations. (3) Simulated distillation by gas chromatography. (4) Equilibrium Flash Vaporization (4) Humpel distillation

Unfortunately the TBP analyses are costly and time consuming, a TBP analysis takes about 48 hours. That is why it is impractical to use it as a tool for daily monitoring of the crude distillation unit operation. For refineries, which often switch the crude oils, the lack of information about the crude oil quality could negatively impact the optimum operation and in this way the profitability of the crude distillation unit.

To ameliorate these inconveniences other quicker methods have been developed. One such method, used for almost all petroleum fractions, except for heavy fractions, is the ASTM D86 method. In this test, the sample is boiled and the vapors are collected and condensed as they are produced. Vapor temperatures are then recorded as a function of cumulative liquid volume collected. Because no reflux is used and there is only one equilibrium stage, the initial boiling point of this assay is larger and the final point is lower than the one in the TBP curve. Test results are commonly expressed as percent evaporator percent, recovered versus corresponding temperature, either in a table or graphically, as a plot of the distillation curve.

This basic test method of determining the boiling range of a petroleum product by performing a simple batch distillation has been in use as long as the petroleum industry has existed. It is one of the oldest test methods under the jurisdiction of ASTM Committee D02, dating from the time when it was still referred to as the ENGLER DISTILLATION. Since the test method has been in use for such an extended period, a tremendous number of historical data bases exist for estimating end-use sensitivity on products and processes.

Here ASTM D-86 method is used to generate the TBP curve. After performing the experiment, we got the temperature versus fractional volume distilled data. Now to interconvert ASTM D-86 distillation to TBP distillation we use Riazi-Daubert method which is based on a generalized correlation in the following form:

TBP= a(ASTM D-86)b

%Volume Coefficient Coefficient range a, oC Distilled 0 10 30 50 70 90 95 a

0.9177 0.5564 0.7617 0.9013 0.8821 0.9552 0.8177

b
1.0190 1.0900 1.0425 1.0176 1.0226 1.0110 1.0355

20-320 35-305 50-315 55-320 65-330 75-345 75-400

Here a, b depend on the fraction distilled as shown in the table and temperature is used in Kelvin. One can safely extrapolate distillation curve from a set of data that does not cover the full distillation range of an oil by using Riazis distribution model. Regardless of the method for distillation used, Riazis model can easily approximate the boiling point distribution. The model contains two set of equations: (Ti - To)/ To = [Atln(1/(1-xi))/Bt]1/ Bt Y= C1 + C2.X (2) (1)

Where Y= ln[(Ti-To)/ To] ; X=lnln[1/(1-xi)] Bt=1/ C2 ; At= Btexp(C1. Bt)

To = initial boiling point in K; Ti = temperature at which i percent is distilled in K; xi = volume or weight part of distillate.

Thus, the TBP curve is generated by plotting the obtained temperature versus % volume distilled.

Here, ASTM D-86 apparatus is used. The basic components of the distillation unit are the distillation flask, the condenser and associated cooling bath, a metal shield or enclosure for the distillation flask, the heat source, the flask support, the thermometer, and the receiving cylinder to collect the distillate.

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We are generating TBP curve for hexane and diesel here using

ASTM D-86 apparatus.

In this test 100 ml of the sample is distilled in a standard flask. The

distillate is condensed in a brass tube condenser, surrounded by water bath kept at 0 oC by ice-water mixture.

First drop from the condenser must be available in 5 mins for

Hexane and 10 mins for Diesel after heating started, at which the recorded temperature is mentioned as Initial Boiling Point (IBP) of the sample. The vapor temperature is recorded at each successive 10 ml

distillate collected in the measuring cylinder.

The test continues in the same way till 95% of fraction is

condensed.

At this point the heat intensity can be increased to obtain the

maximum boiling point also known as End Point (EP).

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Fluctuation in temperatures is common when last 2-3 ml of sample

are distilled. When bottom of the flask shows dryness, the temperature corresponds to final boiling point. The distillate collected should be greater than 95 ml and the difference is accounted as loss; usually ascribed to light ends.

To reduce evaporation loss of the distillate, cover the receiving

cylinder with a piece of blotting paper, or similar material, that has been cut to fit the condenser tube snugly. If a receiver deflector is being used, start the distillation with the tip of the deflector just touching the wall of the receiving cylinder. If a receiver deflector is not used, keep the drip tip of the condenser away from the wall of the receiving cylinder. Note the start time. Observe and record the IBP to the nearest 0.5C (1.0F). If a receiver deflector is not being used, immediately move the receiving cylinder so that the tip of the condenser touches its inner wall.

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VOLUME in ml

TEMPERATURE In Kelvin

(ASTMD-86)b

TBP= a(ASTMD86)b

0 10 20 30 40 50 60 70 80 85

483.15 513.15 523.15 543.15 553.15 563.15 593.15 603.15 613.15 617.15

543.3498376 899.8421311 792.0183019 709.8292227 668.7523888 629.5570221 674.3807141 697.0484161 682.9640656 674.8032484

498.6321459 500.6721618 521.9796619 540.6769189 556.0676113 567.419744 601.3452828 614.8664078 627.4049388 632.2400335

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VOLUME in ml

TEMPERATURE In Kelvin

(ASTMD-86)b

TBP= a(ASTMD86)b

0 10 20 30 40 50 60 70 80 85 90 95 100

328.15 339.15 341.15 342.15 343.15 343.65 343.65 343.65 344.15 345.15 347.15 357.15 363.15

366.3344693 572.9636698 502.056977 438.4506795 408.9547883 380.8482777 386.4490881 392.1322648 379.6340311 374.3571973 376.5566817 387.5567261 394.1588159

336.1851424 324.5266226 330.8806507 333.9678826 340.0459065 343.2585527 344.5966519 345.8998708 348.7508027 350.7446171 352.805369 363.1115856 369.2972486

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As mentioned earlier in Principles the temperature observed in ASTM distillation experiment is converted into TBP data by using Riazi Daubert correlation , which is: TBP= a(ASTM D-86)b The values of coefficient a and b are taken as per table mentioned earlier.We also observe that data for volumes 85-100 ml is not given in the observation table of Diesel. Due to limitation of the thermometer, distillation was performed for temperature not higher than 350 oC. So, we use Riazis Distribution Model to extrapolate the data obtained and get TBP data for 90, 95, 100 ml. Plotting : Y= C1 + C2.X Where Y= ln[(Ti-To)/ To] ; X=lnln[1/(1-xi)] Bt=1/ C2 ; At= Btexp(C1. Bt) To = initial boiling point in K; Ti = temperature at which i percent is distilled in K; xi = volume fraction of distillate.
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The graph obtained is:

0 -2.5 -2 -1.5 -1 -0.5 0 0.5 1

-0.2

-0.4

-0.6

-0.8

-1

-1.2

y = -0.2507x - 0.9118

-1.4

Using linear regression we get the straight line and hence the constants Bt=1/ C2 = -3.0988883 ; At= Btexp(C1. Bt)= -52.27953 .

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Diesel: Initial Boiling Point obtained is around 498 K. End Point obtained is around 666 K. True Boiling Point Plot is as shown:

690

660 T e 630 m p 600 e r a 570 t u r 540 e

Series1

510

(
K

) 480 450
0 10 20 30 40 50 Volume(ml) 60 70 80 90 100

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Hexane: Initial Boiling Point obtained is 336 K. End Point obtained is around 370 K. True Boiling Point Plot is as shown:

380

370

T e m 360 p e r a 350 t u r e 340

( K ) 330 320 0 10 20 30 40 50 Volume (ml) 60 70 80 90 100

Series1

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In the current economic climate, refineries face the heavy task of improving the efficiency of individual units. The lack of crude oil distillation data may result in wide swings in product qualities. The single and most important laboratory analysis is true boiling point distillation, which tends to separate individual mixtures sharply and thus give a very good approximation of the expected separation. Obtaining TBP data is costly and time consuming, however, requiring use of expensive laboratory equipment. A single TBP distillation can take up to 48 hr, which makes it impractical for daily monitoring of refinery crude quality. The Engler distillation (ASTM D-86) is a fast and low cost method for measuring distillation characteristics of oils. It is performed at atmospheric pressure, and for that reason the maximum temperature at which the distillation is terminated is about 360o C. Hence, a full-range distillation curve can be generated from an incomplete distillation data set. Specifically, the full-range crude true boiling point (TBP) curve can be generated from only the atmospheric part of the crude distillation analysis. An improvement in the speed of generating the full-range crude TBP curve can be achieved by converting the ASTM D-86 distillation data of the crude fraction into TBP and applying Riazi's boiling point distribution model. With this approach, the crude oil curve TBP can be

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generated in 45 min instead of the 48 hr typically necessary for crude oil TBP analysis. The method can be used in refineries that frequently run on different crudes for generating the full crude oil TBP curve from the simple and quick ASTM D-86 analysis of the distillation characteristics of the crude fraction.

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1.B.K. Bhaskara Rao, Modern Petroleum Refining Process , Department of Chemical Engineering IIT Kharagpur. 2. Angel Nedelchev, Dicho Stratiev, Atanas Ivanov, Georgy Stoilov ,BOILING POINT DISTRIBUTION OF CRUDE OILS BASED ON TBP AND ASTM D-86 DISTILLATION DATA, Lukoil Neftochim Bourgas Chief Process Engineer Department, 8104 Bourgas, Bulgaria

3. ASTM D86: Standard Test Method for Distillation of Petroleum Products at Atmospheric Pressure. 4. Dr. Khalid Farhod Chasib Developed Equation for fitting ASTM Distillation curves, Chemical Engineering Department - University of Technology.

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