Integration Naphtha De-aromatization

Aromatic components in naphtha are the most undesirable components as they have no ethylene potential. Yet aromatics contribute heavily to furnace fouling (1). Thus removing aromatics is desirable, if it is economical. Aromatics recovery by extraction is a well established technology. Major licensors are UOP, Krupp-Uhde and GTC. Todays mega-size naphtha crackers are designed with dedicated aromatics extraction unit to recover aromatics from the pyrolysis gasoline by-product. Combining aromatic extraction from pyrolysis gasoline and feed naphtha offers an economy of scale which would make de-aromatization of feed naphtha economically feasible. Details of this integration are presented elsewhere (1, 2) and summary is presented below. Naphtha de-aromatization is evaluated using naphthas presented in the Table 1 and the Figure 1 presents a economic analysis indicating a payout period of less than a year. Therefore existing naphtha crackers can enhance their profitability by revamping aromatics extraction unit to handle feed naphtha. Alternately grassroots ethylene crackers can be designed to incorporate naphtha feed dearomatization with pyrolysis gasoline. Obviously details of the integration strategy are important in successful implementation. Table 1 Selected Naphthas Open Naphtha Naphtha Dearomatized Dearomatized Naphtha A B Naphtha Spec A B Naphtha (OSN) Wt% Wt% Wt% Wt% Wt% N-Paraffins 31.90 25.00 20.00 32.89 26.67 I-Paraffins 34.43 30.00 21.00 39.47 28.00 Naphthenes 24.27 21.00 34.00 27.63 45.33 Aromatics 9.4 24.00 25.00 0.00 0.00 Total 100.00 100.00 100.00 100.00 100.00 Specific gravity 0.6987 0.7230 0.7417 0.6862 0.7069 Paraffins 66.33 55.00 41.00 72.36 54.67 Paraffins+Naphthenes 90.60 76.00 75.00 100.00 100.00 Naphtha

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Figure 1 - Integration of Cracker with Aroamtics Extraction Unit

Naphtha Case Base 1 2 kTA Naphtha 2,456 Design 1,964 Design 1,964 Design N-Paraffins Products I-Paraffins Naphthenes Aromatics Case Design vol% 34.8 36.0 21.7 7.5 A vol% 28.2 32.4 19.4 20.0 B vol% 23.1 23.3 32.3 21.3

Cracker

Aromatics Extraction

Case Base 1 2

kTA Naphtha Aromatic rich 604 A naphtha 648 B

Hydrotreater

Base $MM/yr Gross Margin(GM) 209.6 Delta GM Base NHT+A Extr Cost 10.5 Delta Cost Base Payout period,yrs

1 2 $MM/yr $MM/yr 241.8 247.7 32.2 38.1 34.9 36.3 24.4 25.8

0.8

0.7

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The effect of de-aromatization can be further evaluated in relation to the heavy naphtha furnace performance. It is very common to see that operating heavy naphtha is richer in aromatics than the design heavy naphtha. Richer the naphtha in aromatics lower the ethylene yield (1). Consequently furnaces become a bottleneck for ethylene production. To make up for the shortfall in ethylene production an additional furnace could be required. Addition of a heavy naphtha furnace is expensive and it eats into furnace plot space reserved for expansion. .If naphtha furnaces could be de-bottlenecked then addition of a new furnace would be avoided. De-aromatization of heavy naphtha can de-bottleneck existing furnaces thereby avoiding addition of extra furnace capacity. The Table 2 lists characterization of design, operating and de-aromatized heavy naphthas. The Table 3 shows heavy naphtha performance at fixed cracking severity of P/E = 0.55 and fixed firing rate for all three naphthas. As expected, cracking with operating heavy naphtha will need about 8% more feed than the design heavy naphtha with 4% loss in the furnace ethylene capacity Coke lay down increases by 12% and quench exchanger duty increases by 7% with cracking heavy operating naphtha compared to the design heavy naphtha. Specifically firing per pound of ethylene is higher by 5% using heavy operating naphtha compared to design heavy naphtha. On the other hand, de-aromatized naphtha will need 8% lower feed rate than the design heavy naphtha and also produce 4% more ethylene. Consequently cracking de-aromatized heavy naphtha results in lower coke lay down, quench exchanger duty and firing per pound of ethylene compared to the design heavy naphtha. As a result, cracking de-aromatized naphtha will increase furnace run length, decrease quench oil and quench water duty and de-bottleneck quench oil and quench water towers. Significantly, cracking the heavy operating naphtha will result in a revenue loss of $ 6.6 million /yr/furnace (with a furnace capacity of 25,000 lbs/hr of ethylene) versus revenue gain of $ 6.2 million/yr/furnace with de-aromatized heavy naphtha, a swing of $12.8 million/yr/furnace. Thus de-aromatization of heavy naphtha can help cracker operators who are receiving increasingly aromatic rich heavy naphtha than the design heavy naphtha. References 1. Bhirud, V. L., Improve naphtha quality for olefin cracking, Hydrocarbon Processing, April 2007, page 69 2. Bhirud, V. L., More steam cracker integration options, pgs 67-71, PTQ, Catalysis, 2008

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Table 2 Heavy naphtha characteristics

Heavy Heavy Dearomatized Naphtha Naphtha operating Design Operating naphtha vol% vol% vol% 30.60 27.20 34.00 36.74 32.66 40.82 22.66 20.14 25.18 10.00 20.00 100.00 100.00 100.00 0.7281 0.7440 0.7123

N-P I-P Naphthenes Aromatics

SG

Table 3 Furnace performance at fixed firing

Heavy Heavy Naphtha Naphtha Design Operating 0.55 0.55 1.000 1.08 1.000 0.96 1.000 1.05 1.000 1.12 1.000 1.07 25,000 23,937 (1,063) (531) (4.3) (6.6) Dearomatized operating Naphtha 0.55 0.92 1.04 0.96 0.84 0.93 25,998 998 499 4.0 6.2

Propylene/Ethylene Feed rate Ethylene rate Firing per lb of ethylene Coke laydown TLE Duty

Ratio Ratio Ratio Btu/lb C2Ratio Ratio

Furnace Ethylene capacity lbs/hr Ethylene production gain (loss) lbs/hr Ethylene revenue gain (loss), $0.5/lb $/hr Ethylene revenue gain (loss), $0.5/lb $ MM/yr Ethylene+Propylene revenue gain (loss $ MM/yr

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