CO-CRACKING OF MIXED C4’S AND LPG WITH NAPHTHA IN RAS LANUF

ETHYLENE PLANT -LIBYA

Ahmed M. Eltief -Senior Process Engineer
Raslanuf Oil And Gas Processing Company (Rasco)
P.O. Box 2323
Tripoli - Libya
Fax :- 00218-21-3605174

ABSTRACT

The type of feed stock used in an ethylene plant has a major influence on the steam cracker's

product slate and on the overall plant economics. As the Rasco ethylene plant was designed

based on naphtha feed stock, a considerable amount of Mixed C4 is being produced. Mixed

C4's is always sold at prices well below the price of Naphtha. Hence the co-cracking of this

product with Naphtha is feasible., LPG is produced in the Rasco refinery and its selling

price is usually similar to the naphtha price. When the LPG price descends below the price

of naphtha, especially in summer season, co-cracking with naphtha becomes feasible. This

present study, conducted by the Rasco process engineering division, is to evaluate the

impact of the co-cracking of the two products with naphtha on the cracker's yield

distribution and hence on the downstream plant equipment is also evaluated. "PHENICS"

(advanced cracking simulation software) was used to predict the first pass cracker yield in

the following three cases :

1-Naphtha alone(standard case), 2-Naphtha + Mixed C4's, 3- Naphtha+ Mixed C4's+LPG.

Using "HYSIM"(an advanced process simulator), the impact of the changed cracker effluent

composition on the downstream plant units was checked using the naphtha cracking alone as

a base case. The effect of co-cracking on the naphtha pre-heater and on the cracking

furnaces was also determined.

INTRODUCTION

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The type of feed stock used in an ethylene plant has a major influence on the steam cracker's

product slate and on the overall plant economics. Cracking of light feed stocks produces a

higher ethylene yield and the least amounts of co-products. Since such a plant is simple and

straight forward it requires the lowest capital investment. On the other hand cracking of

heavier feed stocks such as naphtha results in the production of large quantities of co-

products and hence an elaborate separation section is required. This is translated to higher

capital investment. Generally an ethylene plant based on heavy feed stock is more suitable

for cracking lighter feed stock than plants feeding ethane only. Moreover, while significant

changes both in equipment and operating conditions are required for an existing ethane-

based plant to change to heavier feed stock such as naphtha, only minor changes are usually

anticipated when lighter feed stocks are introduced in a naphtha or gas oil-based plant.

Under certain conditions, co-cracking of light feed stocks such as propane, butane, or both

in naphtha based plant has merits. This is particularly true when the prices of light olefins

such as ethylene and propylene enjoy greater margin compared to those of heavier products

such as Mixed C4s and pyrolysis gasoline. The relative price of Naphtha and LPG is another

important factor. As the Rasco ethylene plant was designed based on naphtha feed stock, a

considerable amount of Mixed C4 is being produced (about 9 wt. %). Although butadiene

constitutes 45 wt% of this product, mixed C4s is always sold at prices well below the price

of naphtha ( typically naphtha price is double the mixed C4s price). Hence the co-cracking

of this product with naphtha is always feasible except when it can be fed to a nearby

butadiene plant.

LPG is produced in the Rasco refinery and its selling price is usually similar to the naphtha

price. When the LPG price descends below the price of naphtha, especially in summer

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season, co-cracking with naphtha becomes feasible. In the case of Ras Lanuf the LPG can be

fed to the ethylene plant in two ways, either by increasing the naphtha "RVP" and hence

maximizing the naphtha product at the account of LPG or by feeding the LPG product from

storage direct to the ethylene plant where it mixes with the naphtha feed.

Although the first method looks straight forward and without cost, the increase in naphtha

RVP is limited as the naphtha is stored and transported at atmospheric pressure and also by

the product specification required in the international market. This present study, conducted

by the Rasco process engineering division, is to evaluate the additional requirements which

will enable the recycle and co-cracking of all the mixed C4's product together with the co-

cracking of all the LPG produced in the Rasco refinery.

The impact of the co-cracking of the two products with naphtha on the cracker's yield

distribution and hence on the downstream plant equipment is also evaluated.

"PHENICS" (advanced cracking simulation software) was used to predict the first pass

cracker yield in the following three cases:-

1 - Naphtha alone (the standard case).

2 - Naphtha + Mixed C4's.

3 - Naphtha + Mixed C4's + LPG.

As the C3 and C4 hydrocarbons are not fully converted, equilibrium recycle flow

rates for these streams needed to be predicted. These required many runs of the program. At

the equilibrium point, the ultimate yield was predicted for the three cases.

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Using "HYSIM" (an advanced process simulator), the impact of the changed cracker

effluent composition on the downstream plant units was checked using the naphtha cracking

alone as a base case.

The effect of co-cracking on the naphtha pre-heater and on the cracking furnaces was also

determined.

BACK GROUND

I- MIXED C4'S AND RESIDUAL C4'S CO-CRACKING :

Most olefin plant operators occasionally crack some of their C4 streams. This can be

residual C4s recycled from Butadiene, MTBE or Butene-1 plants or raw mixed C4's

recycled directly after debutanization. Because the mixed C4s are rich in butadiene (45 wt %

in Rasco case) it is recommended to dilute the recycle stream to a concentration of 10 to 20

% in the naphtha feed. This is to avoid premature furnace run length termination by excess

cocking.

C2 and C3 olefin yields from butadiene are very poor and hence cracking of raw C4's with

high butadiene content should be practiced only as a "LAST RESORT" measure to dispose

of C4 streams. Table (I) compares the C2/C3 olefin yields from various C4 olefins. Table

(II) compares the C2/C3 olefin yields when cracking C4 paraffins.

TABLE (I)

Comparison of C2/C3 olefin yields from various C4 olefins

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 (once through 95 % conversion)

FEED butadiene iso-butene butene-1 butene-2

PRODUCT

Ethylene 5.2 10.5 17.0 11.4

Propylene 3.8 12.9 18.7 15.8

Total 9.0 23.4 35.7 27.2

TABLE (II)

C2/C3 olefin yields when cracking C4's paraffins

(once through 95 % conversion)

FEED N-Butane ISO-BUTANE

PRODUCT

ETHYLENE 39.4 13.7

PROPYLENE 15.4 18.4

TOTAL 54.8 32.1

As can be seen the n-butane is a very attractive olefin feed stock. For this reason C4 streams

are usually hydrogenated or catalytically reformed to increase the n-butane content and

minimize acetylene and butadiene. The influence of recycling C4 fraction to the crackers is

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primarily in the C3 and C4 fractionation systems. When the C4s stream is rich in olefin,

production of C2/C3 acetylene usually increases and hence the related systems need careful

checking. High quantities of methane may also be produced from the cracking of butane.

This may overload the demethanizer system.

In the present case the impact on each plant system has been carefully checked as will be

detailed later in this report.

II- LPG CO-CRACKING :

LPG is a desirable feed stock for thermal cracking due to its high yield of C2/C3 olefins. It

is not commonly cracked because its price is usually higher than lighter and heavier feed

stocks and is generally less available.

16 MT/hr of LPG (78 wt% butane and 20 wt% propane) is produced at Ras Lanuf refinery

and is currently being exported. As the LPG price some times drops below the price

of naphtha, its co-cracking with naphtha may become feasible depending on the

LPG/Naphtha price ratio.

As mentioned earlier, LPG co-cracking in Ras Lanuf can be achieved by either raising the

naphtha RVP in the refinery or by injecting LPG direct into the naphtha feed to the ethylene

plant.

IMPACT OF C4'S AND LPG CO-CRACKING ON FURNACES AND PLANT

SYSTEMS
The objective of this part of the study is to evaluate the change in composition and flow

rate of each major stream in the plant when co-cracking C4s and / or LPG with naphtha and

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then to check whether or not the selected plant systems and equipment can cope with these

changes.

All the yields were predicted at the cracker design coil out-let temperature (823°C for the

naphtha cracking furnaces and 848°C for ethane/propane recycle cracking furnaces) :-

1 - Cracking Furnaces :

1.1 - Yield Distribution

Table (1) shows the overall feed rate and product yields for the three different cases

under consideration. These cases are defined as follows :

CASE 1:- Naphtha Cracking

CASE 2:- Naphtha/Mixed C4 Co-Cracking

CASE 3 :- Naphtha/Mixed C4/LPG Co-Cracking

Flow rates of the feed and the recycle of mixed C4s to the plant are adjusted to give the

same totals. The yields of products for the same coil outlet temperatures show cracking of

mixed C4s to extinction in cases 2 and 3. It should be noted that for basically the same

production amount of ethylene, propylene and pyrolysis gasoline from the plant the feed

reduces by 10.5% and 13.7% in cases 2 and 3 respectively. Mass flow from the furnaces is

the highest in case 3, indicating the highest recycle flows bearing in mind that case 3 has the

lowest plant feed rate. Also in case three we see an increase in the mole fractions of propane,

normal and iso-butanes as would be expected when co-cracking LPG.

TABLE (1)

ETHYLENE PLANT PRODUCTS WITH DIFFERENT FEED STOCKS

CASE 1 CASE 2 CASE 3

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FEED -NAPHTHA 3638 3258 2816

(MT -RECY. C4’S 0 380 445

/DAY) -LPG 0 0 377

TOTAL TO 3638 3638 3638

FURNACE

TOTAL TO 3638 3258 3193

PLANT

WT% MT/DAY WT% MT/DAY WT% MT/DAY

PLANT FUEL GAS 17.00 619 17.46 569 18.13 578.90

YIELD ETHYLENE 28.15 1024 30.31 988 31.31 999.80

AT PROPYLENE 15.21 553 17.22 561 18.68 596.50

823 c MIXED C4’S 09.37 341 00.00 0.0 00.00 0.0

COT PY.GASOLINE 24.89 906 28.96 943 27.04 863.3

FUEL OIL 05.38 195 06.05 197 04.84 154.50

TOTAL 100 3638 100 3258 100 3139

1.2 - Related Problems

The Rasco VMR-8 furnaces are designed to crack both recycle C2 and C3 as well as the

naphtha. Therefore there should be no problems associated with LPG/mixed C4 co-cracking

as the temperatures experienced in the furnaces will fall between the high temperatures

required for recycle cracking and the lower temperatures required for naphtha cracking.

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2 - PRIMARY FRACTIONATION (quench oil & quench water systems) :

In general, based on other plants experience, for a naphtha cracker, increasingly lighter feed

stocks result in lower fuel oil production which causes problems with quench oil viscosity in

the pre fractionation system. This can be overcome in a variety of ways. The use of a flux-

oil addition to maintain quench oil quality has been adopted by several S & W clients. If,

however, this process is uneconomical because of product down grading reasons, or the

unavailability of suitable flux oil, then the plant must be operated with a minimum distillate

(naphtha) feed to satisfy primary fractionator operability. In the cases studied, this is not

expected to be a problem as fuel oil production does not vary much in the three cases. For

both the primary fractionation tower (oil quench) and the water quench tower, the Hysim

models were reviewed and updated as necessary. Simulations for the three cases were

studied. The results show that the loading variations for the three cases are within an

acceptable range.

The effect on quench oil viscosity will be minor.

3 - CRACKED GAS COMPRESSION SYSTEM :

The Hysim model for the cracked gas compressor was reviewed and updated. Simulations

for the three different feed cases were carried out. The horse power requirement is more in

case 3 than in case 1. Case 2 has the lowest horse power requirement. Referring to the Stone

and Webster data sheet, the vendor compressor data ((Dresser Rand (D-R)) and the Hysim

(H), as total power calculated by Dressere Rand (by using data from manual as supplied by

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stone and webster) is 6% grater than Hysim calculated power., it is concluded that clean

compressor can handle the three feed cases.

Also the impact on the inter-stage equipments was checked, No bottleneck is expected.

4 - DEMETHANIZER SYSTEM :

The demethanizer and cold box system computer model was reviewed and updated.

Simulation for the three different cases were made and studied. The impact on the cold box

system and the demethanizer feed separation drums is reviewed.

The computer simulation indicates that changes will be within normal design margins.

However the reported current operating apparent bottleneck at drum 1-M-29 (demethanizer

4th. Feed drum) needs further investigation.

The impact of the alternate cases in the demethanizer tower is reviewed. The tower sections

loading varies from design but is generally within design limitations.

5 - DEETHANIZER TOWER :

The deethanizer tower was simulated with the three different feed cases. The tower sections

loading variations for the three different feeds were extracted.

The deethanizer tower sections loading varied a little bit but still within normal design

allowances.

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6 - DEPROPANIZER & DEBUTANIZER TOWERS :

Both towers were simulated with the three different feeds, and the towers sections loading

variations are reviewed. Because C3s and C4s are not fully converted/cracked in cracking

furnaces, the unconverted portion will be recycled. Propane will be recycled to be cracked

with the ethane in the recycle cracking furnace. Unconverted C4s will be recycled via the

debutanizer to be co-cracked with naphtha.

The section subjected to the greatest change in the depropanizer tower is the stripping

section were the C4s are concentrated. The depropanizer overhead section will be

overloaded by 2.27% in case 2 and 9.54% in case 3. The bottom section of the depropanizer

will be overloaded by 4.68% in case 2 and by 15.56% in case 3.

Referring to stripper bottom pump (1-P-27 A/B) data sheet, the pump design margin can

accommodate this 15.56% overload.

Referring to the depropanizer data sheet, the design allowance is 15%, hence no bottle neck

expected for the depropanizer tower.

The debutanizer overhead section will be overloaded by 10.15% in case 2 and by 30.64% in

case 3.

Referring to the debutanizer data sheet, the design allowance is 15%, so the debutanizer

tower overhead section is expected to be the bottle neck in case 3.

Previous studies using Hysim Simulations have shown that towers in the plant including the

debutanizer have too many trays. This causes the products from the towers to be too pure

when using the reflux and boil-up rates suggested by the designer. Simulation on Hysim

shows that the reflux ratio can be reduced from 1.5 to 1.1 (with the corresponding reduction

in boil-up rates) and still achieve the required product specifications. This reduces the

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internal liquid and vapour traffic inside the column and brings the column back into

operating range for

case 3.

7 - ACETYLENE :

Acetylene’s content in the C2 and C3 streams is increased but the expected hydrogen

needed for hydrogenation in both the C2 and C3 hydrogenation reactors will not exceed 6 %

of total hydrogen production. No problems are hence expected in the reactors or hydrogen

demand.

8 - ETHYLENE & PROPYLENE TOWERS :

The towers were simulated for the three different cases feed and the tower section loading

variations are reviewed. Load changes are generally within the design margins for the

towers and no bottlenecks are expected.

9 - GASOLINE TREATMENT UNIT :

The gasoline treatment unit feeds for the three different cases do not vary much.

The C5s, C6 - C8 and C9s content in the feed to the gasoline treatment unit for the three

case reviewed. No large variations are indicated.

10- NAPHTHA FEED PRE-HEATER, 1-T-14 :

The heater streams were simulated for the three cracking furnaces feed cases, and the heat

exchanger rated using the software "STX". The results shows that the heat exchanger area is

oversized for the three cases, so no bottleneck is expected.

Also there is no vaporisation of the feed stream in any of the three cases.

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CONCLUSIONS

There is always a design allowance on equipment, (up to 15% on certain main equipment

and 20% on reflux systems). Therefore some operating parameter can be adjusted to

compensate for increased flows or changed compositions.

These adjustments encompass such things as; increasing overhead recycle vents in some

distillation towers to reduce the load on the condenser and overhead section; reducing the

reflux ratio will reduce the load on all the tower. Based on these possibilities and on the fact

that the study results show the variation of streams flow rates and equipment loading is not

too great, it is concluded that no bottlenecks are expected when changing the plant feed to

that specified in case 2 (NAPHTHA / MIXED C4'S CO-CRACKING).

In case 3 (NAPHTHA / MIXED C4'S + LPG CO-CRACKING), the debutanizer tower is

expected to be a bottleneck. To overcome this bottle neck, the tower should be operated with

a lower reflux ratio instead of the design reflux ratio.

Even if there is a doubt about bottlenecks the C4's recycle system can still be installed and if

when used a bottleneck became apparent the associated system can then be modified while

the C4's can only be partially recycled.

References

1-Phenics (Advanced cracking simulation software) Manual.

2- 6th. Ethylene forum by Stone & Webster Engineering.

3- 7th. Ethylene forum by Stone & Webster Engineering.

4- Rasco, Process Engineering Division Files.

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